CN106268803A - A kind of preparation method of the graphene-supported Ag Bi photocatalyst with 40 shape of octahedron - Google Patents

A kind of preparation method of the graphene-supported Ag Bi photocatalyst with 40 shape of octahedron Download PDF

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Publication number
CN106268803A
CN106268803A CN201610571532.XA CN201610571532A CN106268803A CN 106268803 A CN106268803 A CN 106268803A CN 201610571532 A CN201610571532 A CN 201610571532A CN 106268803 A CN106268803 A CN 106268803A
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liquid
graphene
photocatalyst
silver nitrate
octahedron
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谢文菊
陈培珍
吴方棣
杨自涛
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Wuyi University
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Wuyi University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66Silver or gold
    • B01J23/68Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/681Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
    • 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
    • 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
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The preparation method of a kind of graphene-supported Ag Bi photocatalyst with 40 shape of octahedron, comprises the following steps: is 1. joined by Graphene in the nitration mixture of concentrated sulphuric acid and concentrated nitric acid, filters after 2 ~ 8 hours, and washing is dried, obtains modified graphene;2. silver nitrate, bismuth nitrate being dissolved in dehydrated alcohol, obtain the mixed solution of silver nitrate and bismuth nitrate, modified graphene step 1. prepared joins in the mixed solution of silver nitrate and bismuth nitrate, and ultrasonic disperse obtains A liquid;3. NaOH is dissolved in 70 ~ 75% ethanol, obtains B liquid;4. under stirring condition, B drop is entered in A liquid, obtain C liquid;5. in C liquid, add CTAB and serine, be transferred to after stirring in reactor, hydro-thermal reaction 2 ~ 4h at 180 ~ 200 DEG C, filter, wash, i.e. obtain the graphene-supported Ag Bi photocatalyst with 40 shape of octahedron after drying.

Description

A kind of graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron Preparation method
Technical field
The invention belongs to organic pollutant degradation technique field, be specifically related to a kind of graphene-supported have 48 The preparation method of the Ag-Bi photocatalyst of face bodily form looks.
Background technology
Process the Organic substance in industrial wastewater, waste gas with the method for photocatalytic degradation, attract people's attention in recent years, pass through Structure and morphology control and doping etc. can be improved the photocatalysis performance of catalyst, grinding at photocatalysis degradation organic contaminant In studying carefully, metal dispersity and the catalyst dispersion situation in dye solution is all to affect its light degradation dye molecule catalysis activity Key factor.Nano-photocatalyst material is than general catalysis material major embodiment on the active function promoting light-catalyzed reaction At two aspects: one is from the point of view of above-mentioned photocatalytic mechanism, and light induced electron and hole are depended in oxidation, the power of reduction Concentration.Obviously photocatalyst granular size is the least, and total surface area is the biggest, and efficiency of light absorption is the highest, and electronics and hole are moved The biggest to the probability on surface.Powder graphite alkene is big because of its specific surface area, is increasingly becoming the focus of research so that photocatalysis technology Application in water treatment field is possibly realized.Since 20 century 70s, utilize metal photocatalysts oxidation water pollutant Work is paid attention to by people day by day, and its advantage essentially consists in: first, utilizes metal photocatalysts oxidative degradation water pollutant not The water being same as simple physical method, chemical method and biological method processes, and handling process is simple, non-secondary pollution, processes speed Spend faster than microbial method;Secondly, metal photocatalysts oxidation can process various inorganic and organic pollution and make its mineralising, is one Plant oxidation treatment method, it is crucial that Photocatalytic Oxidation is possible with sunlight resource, energy-conservation and pollution-free.
Summary of the invention
It is an object of the invention to provide the graphene-supported tool that a kind of degradation rate to rhodamine B is high, degradation time is short There is the preparation method of the Ag-Bi photocatalyst of 40 shape of octahedron.
For achieving the above object, the technical solution used in the present invention is: a kind of graphene-supported to have 40 octahedra The preparation method of the Ag-Bi photocatalyst of pattern, comprises the following steps: 1. Graphene is joined at 85 ~ 100 DEG C concentrated sulphuric acid with In the nitration mixture of concentrated nitric acid, Graphene and the weight ratio 0.5 ~ 21 of nitration mixture, filter after 2 ~ 8 hours, washing, be dried, obtain modified graphite Alkene;2. silver nitrate, bismuth nitrate are dissolved in dehydrated alcohol, obtain the mixed solution of silver nitrate and bismuth nitrate, silver nitrate and nitric acid In the mixed solution of bismuth, the concentration of silver nitrate is 0.3 ~ 1mol/L, and modified graphene step 1. prepared is by solid-to-liquid ratio 1g 20ml ~ 1g 30ml joins in the mixed solution of silver nitrate and bismuth nitrate, and ultrasonic disperse 1 ~ 2h obtains A liquid;3. NaOH is dissolved in 70 ~ 75%(volume fraction) in ethanol, obtain B liquid, in B liquid, the concentration of NaOH is 1.5 ~ 2mol/L;4. by B liquid under stirring condition Instilling in A liquid, obtain C liquid, wherein, in B liquid, in NaOH Yu A liquid, the mol ratio of silver nitrate is 2 ~ 41;5. add in C liquid CTAB and serine, be transferred to after stirring in reactor, hydro-thermal reaction 2 ~ 4h at 180 ~ 200 DEG C, filters, washs, is dried After i.e. obtain the graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron.
Preferably, described step 2. middle silver nitrate, the mol ratio of bismuth nitrate is 1 ~ 31.
Preferably, described step 5. middle CTAB is 1 ~ 1.5 1 with the mass ratio of serine, and the solid-to-liquid ratio of CTAB Yu C liquid is 8 ~ 10g 1L.
Preferably, described step 1. middle concentrated sulphuric acid is 2 ~ 41 with the volume ratio of concentrated nitric acid;The concentration of concentrated sulphuric acid is 98wt%, The concentration of concentrated nitric acid is 69wt%.
The beneficial effect comprise that: by by Ag-Bi photocatalyst on Graphene, it is to avoid common Ag-Bi photocatalyst size compared with big, dispersibility is poor, shortcoming of easily reuniting;By adding CTAB and serine, anti-in conjunction with hydro-thermal Answer condition, prepared the Ag-Bi photocatalyst of the higher 40 graphene-supported shape of octahedron of selectivity, by controlling The ratio of Ag-Bi, this photocatalyst degradation rate to rhodamine B under ultraviolet source demonstrates and is well catalyzed activity, has It is widely applied prospect.
Accompanying drawing explanation
Fig. 1 is the transmission of the graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron of embodiment 1 preparation Electromicroscopic photograph;
The XRD figure of the graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron that Fig. 2 is prepared for embodiment 1;
Fig. 3 is that the graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron of embodiment 1 preparation is to rhodamine B Degradation effect figure;
Fig. 4 is the transmission electron microscope photo of the graphene-supported Ag-Bi photocatalyst of control experiment 1 preparation.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
The preparation method of a kind of graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron, comprises the following steps: 1. Graphene joins at 90 DEG C the nitration mixture of concentrated sulphuric acid and concentrated nitric acid, and (concentrated sulphuric acid is 31 with the volume ratio of concentrated nitric acid, concentrated sulphuric acid Concentration be 98wt%, the concentration of concentrated nitric acid is 69wt%) in, the weight ratio of Graphene and nitration mixture filtered after 11,5 hours, washed Wash, be dried, obtain modified graphene;2. silver nitrate, bismuth nitrate (silver nitrate, the mol ratio of bismuth nitrate are 1 1) are dissolved in anhydrous second In alcohol, obtaining the concentration of silver nitrate in the mixed solution of the mixed solution of silver nitrate and bismuth nitrate, silver nitrate and bismuth nitrate is 0.5mol/L, the mixing that modified graphene step 1. prepared joins silver nitrate and bismuth nitrate by solid-to-liquid ratio 1g 25ml is molten In liquid, ultrasonic disperse 1h, obtain A liquid;3. being dissolved in 70% ethanol by NaOH, obtain B liquid, in B liquid, the concentration of NaOH is 1.5mol/ L;4. being entered in A liquid by B drop under stirring condition, obtain C liquid, wherein, in B liquid, in NaOH Yu A liquid, the mol ratio of silver nitrate is 4 1;5. (CTAB is 1.2 1 with the mass ratio of serine, and the solid-to-liquid ratio of CTAB with C liquid is to add CTAB and serine in C liquid 8g 1L), it is transferred to after stirring in reactor, hydro-thermal reaction 4h at 200 DEG C, filters, wash, i.e. obtain Graphene after drying The Ag-Bi photocatalyst with 40 shape of octahedron of load.
Reference examples 1
Reference examples 1 is with the difference of embodiment 1, step 5. in be added without CTAB and serine, C liquid is directly proceeded to instead Answer in still, hydro-thermal reaction 4h at 200 DEG C, filters, washs, is dried.
Reference examples 1 preparation graphene-supported Ag-Bi photocatalyst as shown in Figure 4, from fig. 4, it can be seen that prepare Photocatalyst pattern be irregularly shaped.
Embodiment 2
The preparation method of a kind of graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron, comprises the following steps: 1. Graphene joins at 85 ~ 100 DEG C the nitration mixture of concentrated sulphuric acid and concentrated nitric acid, and (concentrated sulphuric acid is 31 with the volume ratio of concentrated nitric acid, dense The concentration of sulphuric acid is 98wt%, and the concentration of concentrated nitric acid is 69wt%) in, the weight ratio of Graphene and nitration mixture mistake after 21,8 hours Filter, washing, it is dried, obtains modified graphene;2. silver nitrate, bismuth nitrate (silver nitrate, the mol ratio of bismuth nitrate are 3 1) are dissolved in nothing In water-ethanol, obtain the concentration of silver nitrate in the mixed solution of the mixed solution of silver nitrate and bismuth nitrate, silver nitrate and bismuth nitrate For 0.3mol/L, modified graphene step 1. prepared joins the mixing of silver nitrate and bismuth nitrate by solid-to-liquid ratio 1g 20ml In solution, ultrasonic disperse 1.5h, obtain A liquid;3. being dissolved in 75% ethanol by NaOH, obtain B liquid, in B liquid, the concentration of NaOH is 2mol/L;4. under stirring condition, B drop is entered in A liquid, obtain C liquid, wherein, the mol ratio of silver nitrate in NaOH Yu A liquid in B liquid It is 21;5. (CTAB is 11 with the mass ratio of serine, and the solid-to-liquid ratio of CTAB with C liquid is to add CTAB and serine in C liquid 8g 1L), it is transferred to after stirring in reactor, hydro-thermal reaction 2h at 180 DEG C, filters, wash, i.e. obtain Graphene after drying The Ag-Bi photocatalyst with 40 shape of octahedron of load.
Embodiment 3
The preparation method of a kind of graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron, comprises the following steps: 1. Graphene joins at 85 ~ 100 DEG C the nitration mixture of concentrated sulphuric acid and concentrated nitric acid, and (concentrated sulphuric acid is 31 with the volume ratio of concentrated nitric acid, dense The concentration of sulphuric acid is 98wt%, and the concentration of concentrated nitric acid is 69wt%) in, the weight ratio of Graphene and nitration mixture mistake after 0.5 1,2 hours Filter, washing, it is dried, obtains modified graphene;2. silver nitrate, bismuth nitrate (silver nitrate, the mol ratio of bismuth nitrate are 2 1) are dissolved in nothing In water-ethanol, obtain the concentration of silver nitrate in the mixed solution of the mixed solution of silver nitrate and bismuth nitrate, silver nitrate and bismuth nitrate For 1mol/L, the mixing that modified graphene step 1. prepared joins silver nitrate and bismuth nitrate by solid-to-liquid ratio 1g 30ml is molten In liquid, ultrasonic disperse 2h, obtain A liquid;3. being dissolved in 70% ethanol by NaOH, obtain B liquid, in B liquid, the concentration of NaOH is 1.5mol/ L;4. being entered in A liquid by B drop under stirring condition, obtain C liquid, wherein, in B liquid, in NaOH with A liquid, the mol ratio of silver nitrate is 2.5 1;5. (CTAB is 1.5 1 with the mass ratio of serine, the solid-to-liquid ratio of CTAB Yu C liquid to add CTAB and serine in C liquid For 10g 1L), it is transferred to after stirring in reactor, hydro-thermal reaction 4h at 200 DEG C, filters, wash, i.e. obtain graphite after drying The Ag-Bi photocatalyst with 40 shape of octahedron of alkene load.
Degrading experiment
The graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron of embodiment 1 preparation is at ultraviolet source irradiation Under as follows to the degradation experiment step of rhodamine B: rhodamine B solution 100mL that concentration is 10mg/L is added photocatalysis instrument In reaction tube, it is subsequently adding Ag-Bi photocatalyst 0.02g, the ultrasonic disperse 4min prepared through hydro-thermal reaction, static in darkroom Reach to react adsorption equilibrium after absorption 30min, open ultraviolet source and magnetic stirring apparatus, at interval of 20min in During Illumination Sampling, takes the supernatant rhodamine B maximum absorption wavelength l=554nm at after centrifugation, use 722N visible spectrophotometric Meter measures sample absorbance, and passes through formula: DC=[(A0-Ai)/A0] 100% complete the calculating of degradation rate, it is wherein A0For The absorbance of the rhodamine B solution of 10mg/L, AiThe absorbance of the rhodamine B solution for measuring during timing sampling.At 254nm ripple Irradiating 2 hours under long ultraviolet light, the degradation rate of rhodamine B is 97.8%.

Claims (4)

1. the preparation method of a graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron, it is characterised in that Comprise the following steps: 1. Graphene is joined at 85 ~ 100 DEG C concentrated sulphuric acid with in the nitration mixture of concentrated nitric acid, Graphene and nitration mixture Weight ratio 0.5 ~ 21, filtered after 2 ~ 8 hours, and washing is dried, obtains modified graphene;2. silver nitrate, bismuth nitrate are dissolved in anhydrous In ethanol, obtaining the concentration of silver nitrate in the mixed solution of the mixed solution of silver nitrate and bismuth nitrate, silver nitrate and bismuth nitrate is 0.3 ~ 1mol/L, modified graphene step 1. prepared joins silver nitrate and nitric acid by solid-to-liquid ratio 1g 20ml ~ 1g 30ml In the mixed solution of bismuth, ultrasonic disperse 1 ~ 2h, obtain A liquid;3. NaOH is dissolved in 70 ~ 75% ethanol, obtains B liquid, NaOH in B liquid Concentration be 1.5 ~ 2mol/L;4. under stirring condition, B drop is entered in A liquid, obtain C liquid, wherein, nitre in NaOH Yu A liquid in B liquid The mol ratio of acid silver is 2 ~ 41;5. in C liquid, add CTAB and serine, be transferred to after stirring in reactor, 180 ~ Hydro-thermal reaction 2 ~ 4h at 200 DEG C, filter, wash, i.e. obtain after drying the graphene-supported Ag with 40 shape of octahedron- Bi photocatalyst.
The preparation method of the most graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron, It is characterized in that, step 2. middle silver nitrate, the mol ratio of bismuth nitrate are 1 ~ 31.
The preparation method of the most graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron, It is characterized in that, described step 5. in the mass ratio of CTAB and serine be 1 ~ 1.5 1, the solid-to-liquid ratio of CTAB Yu C liquid is 8 ~ 10g 1L.
The preparation method of the most graphene-supported Ag-Bi photocatalyst with 40 shape of octahedron, It is characterized in that, described step 1. middle concentrated sulphuric acid is 2 ~ 41 with the volume ratio of concentrated nitric acid.
CN201610571532.XA 2016-07-20 2016-07-20 A kind of preparation method of the graphene-supported Ag Bi photocatalyst with 40 shape of octahedron Pending CN106268803A (en)

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CN104096578A (en) * 2014-07-31 2014-10-15 安徽工业大学 Preparation method for an Ag/AgBr/GO nano-composite photocatalyst
CN104308169A (en) * 2014-10-17 2015-01-28 华东师范大学 Manufacturing method of concave silver nanoparticles with high-index crystal face
CN104587918A (en) * 2015-01-30 2015-05-06 河海大学 Silver nano-particle modified carbon ball/graphene composite aero-gel material as well as preparation method and application of material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102615290A (en) * 2011-12-12 2012-08-01 湖南理工学院 Preparation method for Ag/graphene nanometer composite materials
CN104096578A (en) * 2014-07-31 2014-10-15 安徽工业大学 Preparation method for an Ag/AgBr/GO nano-composite photocatalyst
CN104308169A (en) * 2014-10-17 2015-01-28 华东师范大学 Manufacturing method of concave silver nanoparticles with high-index crystal face
CN104587918A (en) * 2015-01-30 2015-05-06 河海大学 Silver nano-particle modified carbon ball/graphene composite aero-gel material as well as preparation method and application of material

Non-Patent Citations (1)

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Title
ZHANG LEI, ET AL.: "Cu2+-assisted synthesis of hexoctahedral Au-Pd alloy nanocrystals with high-index facets", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 *

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