CN108079989A - A kind of Cu/ graphenes type Fenton catalyst - Google Patents
A kind of Cu/ graphenes type Fenton catalyst Download PDFInfo
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- CN108079989A CN108079989A CN201611037682.9A CN201611037682A CN108079989A CN 108079989 A CN108079989 A CN 108079989A CN 201611037682 A CN201611037682 A CN 201611037682A CN 108079989 A CN108079989 A CN 108079989A
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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Abstract
A kind of Cu/ graphenes type Fenton catalyst, can be prepared by one step hydro thermal method, and this time catalyst can realize the synchronous progress that the controllable growth of Cu nano particles and graphene oxide (GO) reduce, in H2O2Under existence condition, when the mass ratio of GO and Cu is 3: 17, by 4h catalytic reactions, Cu RGO catalyst can reach 99.5% to the degradation rate of methylene blue, more than 98.1%, Cu RGO catalyst is remained to the degradation rate of methylene blue by 6 recyclings and presents higher catalytic activity and good stability.
Description
Technical field
The present invention relates to a kind of catalyst more particularly to a kind of Cu/ graphenes type Fenton catalysts.
Background technology
Representative of the Fenton oxidation method as high-level oxidation technology, generated hydroxyl radical free radical (OH) almost can be with
Eliminate whole organic pollutions, it is considered to be one of most promising wastewater processing technology.However, there are material profits for Fenton methods
With rate is low, be also easy to produce sludge settling in effective pH narrow ranges and reaction process the defects of, in order to solve problems,
A series of similar Fenton-like technology of mechanism is derived again on the basis of Fenton methods, such as heterogeneous Fenton-like reaction body
System not only remains the advantages of homogeneous reaction process range is wide and reaction speed is fast, while also avoids being lost in because of metal ion
Secondary pollution caused by and.However most Fenton-like catalytic reaction processes are needed by external conditions such as ultrasound, electricity and light, this
Not only bring a large amount of consumption of energy, also add operation difficulty to a certain extent, be unfavorable for Fenton-like technology into
One step is promoted.Therefore, research has a good application prospect with high stability, the type Fenton catalyst of high degradation efficiency.
Copper is a kind of important metallic element, itself is nontoxic, of low cost, be widely used metal material it
One.But Nanometer Copper is easily reunited during preparation and use, and Nanometer Copper is very unstable, is oxidized easily failure.Closely
Nian Lai, the important catalyst component that copper prepares phenol as hydrogen peroxide hydroxylating catalysis benzene has obtained extensive research, in identical item
Under part, Cu/H2O2System is than other transition metal (Ni, Mn, Co etc.)/H2O2System is more prone to OH.
The content of the invention
The purpose of the invention is in order to improve the catalytic activity of Fenton catalyst and stability, devise one kind
Cu/ graphene type Fenton catalysts.
The technical solution adopted by the present invention to solve the technical problems is：
The raw material for preparing of Cu/ graphene type Fenton catalysts includes：Graphite oxide, methylene blue (MB), hydrogen peroxide (H2O2,
Analyze pure), Gerhardite (Cu (NO3)2·3H2O, analysis are pure), sodium hydroxide (NaOH, analysis are pure), absolute ethyl alcohol (point
It analyses pure).
The preparation process of Cu/ graphene type Fenton catalysts is as follows：Cu-RGO catalyst, wherein oxygen are prepared with hydro-thermal method
Graphite alkene (GO) and the mass ratio of Cu are 3: 17, and specific preparation process is as follows：Weigh the Cu (NO of 1000mg3)2·3H2O is dissolved in
In the deionized water of 20mL, pH=10 are adjusted with 10% NaOH solution under fast stirring, are filtered, filter cake is with deionized water and nothing
Water-ethanol washs, and then filter cake is transferred in the beaker of 50mL, by the use of the absolute ethyl alcohol of 20mL as dispersant, ultrasonic 30min
Make it homodisperse.In addition 10mg is taken with graphite oxide made from improving Hummers methods, is added in 50mL absolute ethyl alcohols,
Ultrasound removes the ethanol solution of formation graphene oxide after 30min.Above two system is mixed, with 10% after ultrasonic 10min
NaOH solution adjusts pH=10, in the hydrothermal reaction kettle for stirring the polytetrafluoroethylene (PTFE) for being transferred to 100mL after 30min, 200 DEG C
Lower reaction 10h.Reaction finishes suction filtration, and filter cake is washed with deionized water and ethyl alcohol, and after 60 DEG C of vacuum drying 8h, ground sample is standby
With.
The beneficial effects of the invention are as follows：
Cu/ graphene type Fenton catalysts are in H2O2Under existence condition, when the mass ratio of GO and Cu is 3: 17, urged by 4h
Change reaction, Cu-RGO catalyst can reach 99.5% to the degradation rate of methylene blue, be recycled by 6 times to methylene blue
Degradation rate remains at more than 98.1%, Cu-RGO catalyst and presents higher catalytic activity and good stability.
Description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is influence of the temperature to MB degradation effects.
Fig. 2 is influence of the dioxygen water consumption to MB degradation effects.
Fig. 3 is influence of the catalyst amount to MB degradation effects.
Fig. 4 is the catalytic performance that Cu-RGO catalyst circulations use.
Specific embodiment
Embodiment 1：
The raw material for preparing of Cu/ graphene type Fenton catalysts includes：Graphite oxide, methylene blue (MB), hydrogen peroxide (H2O2,
Analyze pure), Gerhardite (Cu (NO3)2·3H2O, analysis are pure), sodium hydroxide (NaOH, analysis are pure), absolute ethyl alcohol (point
It analyses pure).
The preparation process of Cu/ graphene type Fenton catalysts is as follows：Cu-RGO catalyst, wherein oxygen are prepared with hydro-thermal method
Graphite alkene (GO) and the mass ratio of Cu are 3: 17, and specific preparation process is as follows：Weigh the Cu (NO of 1000mg3)2·3H2O is dissolved in
In the deionized water of 20mL, pH=10 are adjusted with 10% NaOH solution under fast stirring, are filtered, filter cake is with deionized water and nothing
Water-ethanol washs, and then filter cake is transferred in the beaker of 50mL, by the use of the absolute ethyl alcohol of 20mL as dispersant, ultrasonic 30min
Make it homodisperse.In addition 10mg is taken with graphite oxide made from improving Hummers methods, is added in 50mL absolute ethyl alcohols,
Ultrasound removes the ethanol solution of formation graphene oxide after 30min.Above two system is mixed, with 10% after ultrasonic 10min
NaOH solution adjusts pH=10, in the hydrothermal reaction kettle for stirring the polytetrafluoroethylene (PTFE) for being transferred to 100mL after 30min, 200 DEG C
Lower reaction 10h.Reaction finishes suction filtration, and filter cake is washed with deionized water and ethyl alcohol, and after 60 DEG C of vacuum drying 8h, ground sample is standby
With.
Embodiment 2：
Prepare Cu/ graphenes type Fenton catalyst simultaneously tested, in the adsorption process in experiment, c/c0 with temperature reduction
And reduce, show that adsorption process is exothermic reaction, low temperature can promote absorption of the RGO to MB, while Cu-RGO catalyst has MB
There is a good adsorption capacity, the graphene sheet layer in catalyst as carrier passes through electrostatic attraction with MB molecules and π-π are stacked and made
With providing more active adsorption sites for dye molecule.It will be seen from figure 1 that after adding in hydrogen peroxide, with the reaction time
Variation, Cu-RGO catalyst influences clearly the catalytic degradation effect of MB, and c/c0 is gradually dropped with the extension in reaction time
Low, the concentration of MB solution tapers into, and illustrates under Cu-RGO catalyst actions, and H2O2 is fully dissociated into OH groups, and then
Direct oxidation MB simultaneously makes its group decoloration that develops the color.In addition, c/c0 of the reaction temperature at 25 ~ 30 DEG C, which reduces amplitude, is significantly larger than 20
~ 25 DEG C, this is because the rise of temperature promotes the rate that hydrogen peroxide is dissociated into OH free radicals on Cu-RGO catalyst,
And temperature is higher to be promoted faster, so as to add OH free radicals with adsorbing the touch opportunity in the MB on RGO surfaces, and then
Promote the degradation to MB.But temperature is excessively high, can make decomposing hydrogen dioxide solution again for water and oxygen, so as to reduce OH groups
Concentration causes the degradation effect unobvious to MB.Therefore, when reaction temperature is 35 DEG C, MB degradation effects are best.
Embodiment 3：
It prepares Cu/ graphenes type Fenton catalyst and is tested, experimental result such as Fig. 2, figure it is seen that working as Cu-
After RGO catalyst reaches adsorption-desorption balance, H is not added with2O2When, catalyst there is no catalytic degradation effect, and is adding in MB
H2O2Afterwards, the degradation efficiency of MB is with H2O2The increase of amount and stepped up.When dioxygen water consumption is 0.5mL, the drop of MB
Solve fastest, and degradation rate is also than H2O2It is much faster when dosage is 0.3,0.4mL, this is because H2O2It is ionized into
The concentration of OH free radicals obtained larger increase, and then enhance itself and absorption in the MB touch opportunities on RGO surfaces, promote
Into the degradation to MB.However, when dioxygen water consumption further increases, catalyst to the degradation effect of MB then and hardly
Become, this is because the OH free radicals in excessive hydrogen peroxide and system are reacted, it is suppressed that excessive OH free radicals
It is reacted with MB so that catalytic degradation reaction has reached equilibrium state.
Embodiment 4：
It prepares Cu/ graphenes type Fenton catalyst and is tested, experimental result such as Fig. 3, the dosage pair of Cu-RGO catalyst
The influence of MB degradation effects is as shown in Figure 3.During adsorption equilibrium, catalyst amount is more, the graphene pair in catalyst
MB Molecular Adsorption amounts are bigger.And in degradation process, with the increase of catalyst amount, degradation effect has also obtained significantly carrying
It is high.But when the dosage of catalyst is more than 6.5mg, c/c0 is not changed significantly but, this is because the dosage phase of hydrogen peroxide
Together, Cu-RGO catalyst continue increase hydrogen peroxide can not be promoted to be dissociated into OH groups, do not have so as to cause degradation effect
Apparent difference.
Embodiment 5：
It prepares Cu/ graphenes type Fenton catalyst and is tested, experimental result such as Fig. 4, Fig. 4 reflect the cycling of catalyst
Performance, it can be seen from the figure that after 6 times recycle, Cu-RGO catalyst activities do not have significant change, to MB
Degradation rate still above 98%, show that Cu-RGO catalyst has preferable stability, the presence of RGO can effectively reduce copper and receive
The reunion of rice corpuscles and the oxidation resistance for greatly promoting it.
Claims (2)
1. a kind of raw material for preparing of Cu/ graphenes type Fenton catalyst includes：Graphite oxide, methylene blue (MB), hydrogen peroxide
(H2O2, analyze pure), Gerhardite (Cu (NO3)2·3H2O, analysis are pure), sodium hydroxide (NaOH, analysis are pure), anhydrous second
Alcohol (analysis is pure).
2. Cu/ graphenes type Fenton catalyst according to claim 1, it is characterized in that：Preparation process is as follows：With hydro-thermal
Method prepares Cu-RGO catalyst, and wherein graphene oxide (GO) and the mass ratio of Cu is 3: 17, and specific preparation process is as follows：It weighs
Cu (the NO of 1000mg3)2·3H2O is dissolved in the deionized water of 20mL, under fast stirring with 10% NaOH solution adjust pH=
10, it filters, filter cake is washed with deionized water and absolute ethyl alcohol, then filter cake is transferred in the beaker of 50mL, with the nothing of 20mL
For water-ethanol as dispersant, ultrasonic 30min makes it homodisperse；In addition 10mg is taken to improve oxidation made from Hummers methods
Graphite is added in 50mL absolute ethyl alcohols, and ultrasound removes the ethanol solution of formation graphene oxide after 30min；By above two
System mixes, and pH=10 are adjusted with 10% NaOH solution after ultrasonic 10min, and poly- the four of 100mL is transferred to after stirring 30min
In the hydrothermal reaction kettle of vinyl fluoride, 10h is reacted at 200 DEG C；Reaction finishes suction filtration, and filter cake is washed with deionized water and ethyl alcohol, and 60
DEG C vacuum drying 8h after, ground sample is spare.
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| CN201611037682.9A CN108079989A (en) | 2016-11-23 | 2016-11-23 | A kind of Cu/ graphenes type Fenton catalyst |
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| CN201611037682.9A CN108079989A (en) | 2016-11-23 | 2016-11-23 | A kind of Cu/ graphenes type Fenton catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111151250A (en) * | 2019-12-30 | 2020-05-15 | 肇庆学院 | Preparation method of fluorescent copper nanocluster-carbon composite catalyst |
-
2016
- 2016-11-23 CN CN201611037682.9A patent/CN108079989A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111151250A (en) * | 2019-12-30 | 2020-05-15 | 肇庆学院 | Preparation method of fluorescent copper nanocluster-carbon composite catalyst |
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