CN109821573A - A kind of water oxidation catalyst and preparation method and purposes - Google Patents
A kind of water oxidation catalyst and preparation method and purposes Download PDFInfo
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- CN109821573A CN109821573A CN201910118208.6A CN201910118208A CN109821573A CN 109821573 A CN109821573 A CN 109821573A CN 201910118208 A CN201910118208 A CN 201910118208A CN 109821573 A CN109821573 A CN 109821573A
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Abstract
The invention belongs to chemical catalyst technical field, a kind of water oxidation catalyst and preparation method and purposes are refered in particular to.Using graphene oxide as outer membrane, in aqueous solution, using the coordination of binding force and p-aminobenzoic acid and Fe (III) and Eu (III) ion between graphene oxide and p-aminobenzoic acid, the stable photaesthesia catalyst (PPaba-Fe with greater activity is successfully synthesized2O3/Eu@GO).This photaesthesia catalyst (PPaba-Fe2O3/ Eu@GO) size be 400nm, can be used for catalytic water oxidation generate O2.The catalyst stable chemical performance, is easily recycled, and is a kind of novel optical drive water oxidation catalyst for integrating photosensitizer, catalyst and electron acceptor.
Description
Technical field
The invention belongs to chemical catalyst technical fields, refer in particular to a kind of rear-earth-doped graphene oxide cladding polyaniline first
Sour nano iron oxide catalyst and preparation method and the application in catalytic water oxidation.
Background technique
Energy environment issues become increasingly conspicuous now, and the catalyst that development converts light energy into chemical energy promotes water oxygen
Oxygen and hydrogen is cracked into be of great significance to the research and development of new energy.In nature, the photosynthetical system of green plants
It is main to promote the electronics transfer of oxygen compound to be catalyzed H using solar energy2The oxidation of O.Manual simulation's photosynthesis carries out optical drive
Water oxygen is converted into oxygen and is of great significance in terms of the research of new energy and the development of Green Chemistry.In recent years, Zhong Duojin
Belong to oxide and has been widely used for catalytic water oxidation [Dau, H.；Fujita,E.；Sun,L.C.Artificial
photosynthesis:beyond mimicking nature.Chem.Sus.Chem.2017,10,4228–4235；Wang,
S.J.；Li,M.；Patil,A.J.；Sun,S.Y.；Tian,L.F.；Zhang,D.X.；Cao,M.W.；Mann,S.Design
and construction of artificial photoresponsive protocells capable of
converting day light to chemical energy.J.Mater.Chem.2017,5(47),24612-
24616.].But since the missing of electron acceptor and light absorber limits the development of metal oxide.Polymer is as a kind of
Novel semi-conductor receives extensive concern；Wherein, polyaniline as a kind of n-type semiconductor can be used as catalyst electron acceptor [Gu,
B.；He,S.；Zhou,W.；Kang,J.C.；Cheng,K.；Zhang,Q.H.；Wang,Y.Polyaniline supported
iron catalyst for selective synthesis of lower olefins from
syngas.J.Energy.Chem.2017,26(4),608-615.].Iron oxide is a kind of potential photocatalysis water oxidation catalysis
Agent.The research discovery p-aminobenzoic acid of our early periods can form polyaniline formic acid, polyaniline formic acid under the action of iron ion
The iron oxide of cladding has the catalyst and electron acceptor of catalysis oxidation, but such catalyst needs noble metal bipyridyl ruthenium conduct
Photosensitizer limits its further utilization.
Summary of the invention
In view of the above-mentioned problems, the present invention passes through the combination and coordination of graphene using rare earth element and ferro element as raw material
The concept of polymerization is prepared for a kind of novel non-ruthenium class optical drive water oxidation catalyst, and is successfully applied to the water of optical drive
Oxidation release oxygen.The catalyst is one kind novel set electron receptor and light absorber in the green catalyst of one, it is expected to be transported
For low-oxygen environment.
The present invention provides a kind of preparation methods of the catalyst of High-efficient Water oxidation.Using graphene oxide as outer membrane, Yu Shui
In solution, the binding force and p-aminobenzoic acid and Fe (III) and Eu between graphene oxide and p-aminobenzoic acid are utilized
(III) coordination of ion successfully synthesizes the stable photaesthesia catalyst (PPaba-Fe with greater activity2O3/Eu@GO)。
This photaesthesia catalyst (PPaba-Fe2O3/ Eu@GO) size be 400nm, can be used for catalytic water oxidation generate O2。
The present invention adsorbs the л-л effect of p-aminobenzoic acid using graphene oxide, then uses p-aminophenyl
Coordination in formic acid between carboxyl and iron ion and rare earth ion europium is while forming ferric oxide nanometer particle, iron ion
P-aminobenzoic acid carries out coordination polymerization and generates polyaniline formic acid, and graphene oxide coats the graphene oxide packet to form europium doping
Polymer nanocomposite ferric oxide catalyst is covered, which turns to O2, and stable chemical performance, it is easily recycled
It utilizes, therefore the catalyst that we prepare is a kind of novel optical drive for integrating photosensitizer, catalyst and electron acceptor
Water oxidation catalyst.
The specific technical solution that the present invention uses is as follows:
A kind of rare earth ion doped graphene oxide cladding poly-p-aminobenzoic acid closes the preparation side of object nano iron oxide
Method carries out as steps described below:
In aqueous solution, p-aminobenzoic acid and sodium hydroxide is added, first time magnetic agitation mixes solution at room temperature
Uniformly, then above-mentioned mixed solution is slowly added into graphene oxide solution, carries out second of magnetic agitation；Add chlorine
Change ferrous solution, carries out third time magnetic agitation；Then Europium chloride aqueous solution is added, carries out the 4th magnetic agitation.It stirs for 4th time
End reaction solution is transferred in reaction kettle after mixing, in 160 DEG C of calcinings 3-12h, best 6h, the oxidation of europium doping can be obtained
The nano iron oxide catalyst of graphene coated.
Wherein the molar ratio of the p-aminobenzoic acid and sodium hydroxide is 2:1-1:2, optimum mole ratio 1:1.
The time of the magnetic agitation is 30min, and temperature is room temperature.
Wherein the molar ratio of the p-aminobenzoic acid and iron chloride is 2:1-1:2, optimum mole ratio 1:1.
Wherein the graphene oxide and iron chloride mass ratio are 1:13.5-1:30, optimum quality ratio 1:27.
Wherein the molar ratio of the Europium chloride and iron chloride is 1:2000-1:5000, optimum mole ratio 1:2500.
Here we report a kind of preparation method of the graphene oxide cladding nano iron oxide of europium doping, we lead to for the first time
Graphene oxide is coated on outer layer while crossing one step hydro thermal method synthesis poly-p-aminobenzoic acid nano iron oxide, increases and urges
The electron transmission efficiency of agent.Simultaneously rare earth ion doped be conducive to improve nano material energy transfer efficiency, can be in nothing
Catalytic water oxidation release oxygen, realizes the function of bionical oxygen evolution under conditions of additional substance, this is in the world to report for the first time
Without using ruthenium be photosensitizer iron-based water oxidation catalyst；Furthermore the present invention utilizes one step hydro thermal method by graphene oxide for the first time
It is coated on rare earth ion doped nano iron oxide outer layer, which improves electronics transfer by introducing graphene oxide
Efficiency, by it is rear-earth-doped improve nano material energy transfer efficiency, obtain it is novel with graphene oxide in outer layer to dilute
The polymer/nanometer iron oxide of native ion doping forms the catalyst of cladding, and this catalyst has preferable catalysis release oxygen to water
Effect has more high catalytic activity and energy transfer efficiency compared with polymer iron oxide.
Detailed description of the invention
Fig. 1 is that PPaba-Fe is prepared in embodiment 12O3The scanning electron microscope (SEM) photograph of/[email protected] figure 1 it appears that
PPaba-Fe2O3/ Eu@GO uniform particle sizes, graphene oxide successfully coat rear-earth-doped nano iron oxide.
Fig. 2 is the PPaba-Fe under LED (4w) light irradiation2O3/ Eu@GO (5mg) reacts release oxygen with water and becomes at any time
Change figure.As can be seen from Fig., under LED light irradiation, catalyst can react release oxygen, in 2 hours experimental periods, oxygen with water
Burst size be stepped up at any time, illustrate the good water oxidation activity of catalyst.
Different Preparation has a certain impact to the amount of catalyst water release oxygen, and what wherein prepared by embodiment 1 urges
Agent activity is best, therefore the sample that performance test uses embodiment 1 to prepare.
Specific embodiment
PPaba-Fe2O3The synthesis of/Eu@GO
1 (PPaba-Fe of embodiment2O3The best preparation method of/Eu@GO): in 5mL aqueous solution, 1mmol p-aminophenyl is added
Formic acid and 1mmol sodium hydroxide (p-aminobenzoic acid and sodium hydroxide molar ratio 1:1), magnetic agitation 30min makes molten at room temperature
Liquid is uniformly mixed.At room temperature, the mixed solution of p-aminobenzoic acid and sodium hydroxide is added in graphene oxide solution,
After magnetic agitation 30min, 1mmol ferric chloride solution is added to (body in the graphene oxide mixed solution of p-aminobenzoic acid
Product is 5mL, wherein iron chloride and p-aminobenzoic acid molar ratio 1:1, graphene oxide and iron chloride mass ratio 1:27), magnetic force
After stirring 30min, 0.4 μm of ol Europium chloride solution is added in above-mentioned mixed solution (Europium chloride and iron chloride molar ratio 1:
2500), after magnetic agitation 30min, 160 DEG C of calcining 6h in reaction kettle are transferred to, the graphene oxide cladding that europium doping can be obtained is poly-
Close object nano iron oxide catalyst.
Embodiment 2: in 5mL aqueous solution, 1mmol p-aminobenzoic acid and 2mmol sodium hydroxide (p-aminophenyl first is added
Acid and sodium hydroxide molar ratio 1:2), magnetic agitation 30min is uniformly mixed solution at room temperature.At room temperature, by p-aminophenyl
The mixed solution of formic acid and sodium hydroxide is added in graphene oxide solution, after magnetic agitation 30min, by 1mmol iron chloride
Solution is added in the graphene oxide mixed solution of p-aminobenzoic acid (volume 5mL, wherein iron chloride and p-aminophenyl first
After sour molar ratio 1:1, graphene oxide and iron chloride mass ratio 1:27), magnetic agitation 30min, by 0.4 μm of ol Europium chloride solution
It is added in above-mentioned mixed solution (Europium chloride and iron chloride molar ratio 1:2500), after magnetic agitation 30min, is transferred in reaction kettle
The graphene oxide coated polymer nano iron oxide catalyst of europium doping can be obtained in 160 DEG C of calcining 6h.
Embodiment 3: in 5mL aqueous solution, 2mmol p-aminobenzoic acid and 1mmol sodium hydroxide (p-aminophenyl first is added
Acid and sodium hydroxide molar ratio 2:1), magnetic agitation 30min is uniformly mixed solution at room temperature.At room temperature, by p-aminophenyl
The mixed solution of formic acid and sodium hydroxide is added in graphene oxide solution, after magnetic agitation 30min, by 1mmol iron chloride
Solution is added in the graphene oxide mixed solution of p-aminobenzoic acid (volume 5mL, wherein iron chloride and p-aminophenyl first
After sour molar ratio 1:2, graphene oxide and iron chloride mass ratio 1:27), magnetic agitation 30min, by 0.4 μm of ol Europium chloride solution
It is added in above-mentioned mixed solution (Europium chloride and iron chloride molar ratio 1:2500), after magnetic agitation 30min, is transferred in reaction kettle
The graphene oxide coated polymer nano iron oxide catalyst of europium doping can be obtained in 160 DEG C of calcining 12h.
Embodiment 4: in 5mL aqueous solution, 1mmol p-aminobenzoic acid and 1mmol sodium hydroxide (p-aminophenyl first is added
Acid and sodium hydroxide molar ratio 1:1), magnetic agitation 30min is uniformly mixed solution at room temperature.At room temperature, by p-aminophenyl
The mixed solution of formic acid and sodium hydroxide is added in graphene oxide solution, after magnetic agitation 30min, by 1mmol iron chloride
Solution is added in the graphene oxide mixed solution of p-aminobenzoic acid (volume 5mL, wherein iron chloride and p-aminophenyl first
After sour molar ratio 1:1, graphene oxide and iron chloride mass ratio 1:15), magnetic agitation 30min, by 0.4 μm of ol Europium chloride solution
It is added in above-mentioned mixed solution (Europium chloride and iron chloride molar ratio 1:2500), after magnetic agitation 30min, is transferred in reaction kettle
The graphene oxide coated polymer nano iron oxide catalyst of europium doping can be obtained in 160 DEG C of calcining 6h.
Embodiment 5: in 5mL aqueous solution, 1mmol p-aminobenzoic acid and 1mmol sodium hydroxide (p-aminophenyl first is added
Acid and sodium hydroxide molar ratio 1:1), magnetic agitation 30min is uniformly mixed solution at room temperature.At room temperature, by p-aminophenyl
The mixed solution of formic acid and sodium hydroxide is added in graphene oxide solution, after magnetic agitation 30min, by 1mmol iron chloride
Solution is added in the graphene oxide mixed solution of p-aminobenzoic acid (volume 5mL, wherein iron chloride and p-aminophenyl first
After sour molar ratio 1:1, graphene oxide and iron chloride mass ratio 1:27), magnetic agitation 30min, by 0.2 μm of ol Europium chloride solution
It is added in above-mentioned mixed solution (Europium chloride and iron chloride molar ratio 1:5000), after magnetic agitation 30min, is transferred in reaction kettle
The graphene oxide coated polymer nano iron oxide catalyst of europium doping can be obtained in 160 DEG C of calcining 3h.
Embodiment 6: the preparation gained of step 1 Example 1 PPaba-Fe2O3/ Eu@GO is scattered in 2mL PB (pH=
8.5) in buffer solution, concentration 2.5mgmL-1, it is transferred in reactor.
For step 2 under illumination condition, every 10min records O2Burst size.
Fig. 2 is the PPaba-Fe under LED (4w) light irradiation2O3/ Eu@GO (5mg) reacts release oxygen with water and becomes at any time
Change figure.As can be seen from Fig., under LED light irradiation, catalyst can react release oxygen, in 2 hours experimental periods, oxygen with water
Burst size be stepped up at any time, illustrate the good water oxidation activity of catalyst.
Claims (6)
1. a kind of water oxidation catalyst, which is characterized in that the water oxidation catalyst is that the graphene oxide cladding of europium doping is poly-
Aniline formic acid nano iron oxide catalyst, the size of the water oxidation catalyst are 400nm, can be used in catalytic water oxidation and generate
O2, it is a kind of optical drive water oxidation catalyst for integrating photosensitizer, catalyst and electron acceptor.
2. a kind of preparation method of water oxidation catalyst as described in claim 1, which is characterized in that specific step is as follows:
In aqueous solution, p-aminobenzoic acid and sodium hydroxide is added, solution is uniformly mixed by first time magnetic agitation at room temperature, then will
Above-mentioned mixed solution is slowly added into graphene oxide solution, carries out second of magnetic agitation；Ferric chloride solution is added, into
Row third time magnetic agitation；Then Europium chloride aqueous solution is added, carries out the 4th magnetic agitation；It will be finally anti-after 4th stirring
It answers solution to be transferred in reaction kettle, in 160 DEG C of calcining 3-12h, the nano oxygen of the graphene oxide cladding of europium doping can be obtained
Change iron catalyst.
3. a kind of preparation method of water oxidation catalyst as claimed in claim 2, which is characterized in that the p-aminophenyl first
The molar ratio of acid and sodium hydroxide is 2:1-1:2；The molar ratio of the p-aminobenzoic acid and iron chloride is 2:1-1:2；Institute
The graphene oxide and iron chloride mass ratio stated are 1:13.5-1:30；The molar ratio of the Europium chloride and iron chloride is 1:
2000-1:5000。
4. a kind of preparation method of water oxidation catalyst as claimed in claim 3, which is characterized in that the p-aminophenyl first
The molar ratio of acid and sodium hydroxide is 1:1；The molar ratio of the p-aminobenzoic acid and iron chloride is 1:1；The oxidation
Graphene and iron chloride mass ratio are 1:27；The molar ratio of the Europium chloride and iron chloride is 1:2500.
5. a kind of preparation method of water oxidation catalyst as claimed in claim 2, which is characterized in that the magnetic agitation when
Between be 30min, temperature is room temperature.
6. a kind of preparation method of water oxidation catalyst as claimed in claim 2, which is characterized in that in 160 DEG C of calcining 6h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382846A (en) * | 1979-08-09 | 1983-05-10 | Engelhard Corporation | Simultaneous production of hydrogen and oxygen from water |
| CN106256432A (en) * | 2016-08-03 | 2016-12-28 | 江苏大学 | A kind of water oxidation reaction catalyst based on metallic organic framework graphene oxide and preparation method thereof |
| US20170106359A1 (en) * | 2009-03-17 | 2017-04-20 | Emory University | Water oxidation catalysts and methods of use thereof |
| CN108070874A (en) * | 2016-11-16 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of water oxidation catalyst that atom disperses and its preparation and application |
-
2019
- 2019-02-15 CN CN201910118208.6A patent/CN109821573B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382846A (en) * | 1979-08-09 | 1983-05-10 | Engelhard Corporation | Simultaneous production of hydrogen and oxygen from water |
| US20170106359A1 (en) * | 2009-03-17 | 2017-04-20 | Emory University | Water oxidation catalysts and methods of use thereof |
| CN106256432A (en) * | 2016-08-03 | 2016-12-28 | 江苏大学 | A kind of water oxidation reaction catalyst based on metallic organic framework graphene oxide and preparation method thereof |
| CN108070874A (en) * | 2016-11-16 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of water oxidation catalyst that atom disperses and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| DONG-LIANG HUANG等: "Polymer United Fe2O3 Nanospheroids for Water Oxidation and the Green Synthesis of 2,3-Dihydrophthalazine-1,4-dione", 《ACS SUSTAINABLE CHEM. ENG.》 * |
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