CN109821573B - A kind of water oxidation catalyst and preparation method and use - Google Patents
A kind of water oxidation catalyst and preparation method and use Download PDFInfo
- Publication number
- CN109821573B CN109821573B CN201910118208.6A CN201910118208A CN109821573B CN 109821573 B CN109821573 B CN 109821573B CN 201910118208 A CN201910118208 A CN 201910118208A CN 109821573 B CN109821573 B CN 109821573B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- aminobenzoic acid
- graphene oxide
- water oxidation
- ferric chloride
- 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
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
本发明属于化学催化剂技术领域，特指一种水氧化催化剂及制备方法和用途。以氧化石墨烯为外膜，于水溶液中，利用氧化石墨烯与对氨基苯甲酸之间的结合力及对氨基苯甲酸与Fe(III)和Eu(III)离子的配位，成功合成了稳定的具有较高活性的光敏感催化剂(PPaba‑Fe2O3/Eu@GO)。这种光敏感催化剂(PPaba‑Fe2O3/Eu@GO)的大小为400nm，可用于催化水氧化产生O2。该催化剂化学性能稳定，易于回收利用，是一类新型的集光敏剂、催化剂和电子受体为一体的光驱动水氧化催化剂。
The invention belongs to the technical field of chemical catalysts, and particularly relates to a water oxidation catalyst and a preparation method and application thereof. Using graphene oxide as the outer film, in aqueous solution, using the binding force between graphene oxide and p-aminobenzoic acid and the coordination between p-aminobenzoic acid and Fe(III) and Eu(III) ions, the stable synthesis was successfully completed. The photosensitive catalyst with high activity (PPaba‑Fe 2 O 3 /Eu@GO). This photosensitive catalyst (PPaba‑Fe 2 O 3 /Eu@GO) with a size of 400 nm can be used to catalyze water oxidation to produce O 2 . The catalyst has stable chemical properties, is easy to recycle, and is a new type of light-driven water oxidation catalyst integrating photosensitizer, catalyst and electron acceptor.
Description
Technical Field
The invention belongs to the technical field of chemical catalysts, and particularly relates to a rare earth doped graphene oxide coated polyaniline formic acid nano iron oxide catalyst, a preparation method and application in water oxidation catalysis.
Background
Nowadays, the development of a catalyst for converting light energy into chemical energy to promote the oxidative cracking of water into oxygen and hydrogen has important significance for the research and development of new energy. In nature, the photosynthetic system of green plants mainly utilizes solar energy to promote electron transfer catalysis H of oxygen complex2And (4) oxidizing O. The artificial simulation of photosynthesis to carry out the oxidation of the driving water by the optical driver to convert the driving water into oxygen has important significance in the research of new energy and the development of green chemistry. In recent years, numerous metal oxides have been widely used to catalyze the oxidation of water [ Dau, h; fujita, e.; sun, L.C.Artificial photosynthesis, beyond and micromiking nature, chem.Sus.chem.2017,10, 4228-; wang, s.j.; li, M.; patil, A.J.; sun, s.y.; tian, l.f.; zhang, d.x.; cao, m.w.; man, S.design and construction of intellectual phosphor technical cells a portable of converting day light to chemical energy J.Mater.chem.2017,5(47),24612 and 24616.]. But the development of metal oxides is limited by the absence of electron acceptors and light absorbers. Polymers have received much attention as a new type of semiconductor; among them, polyaniline, as an n-type semiconductor, can be used as an electron acceptor of a catalyst [ 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 synthesis. J.energy. chem.2017,26(4), 608-.]. Iron oxide is a potential photocatalytic water oxidation catalyst. Before usThe research in the future finds that p-aminobenzoic acid can form polyaniline formic acid under the action of iron ions, and iron oxide coated by the polyaniline formic acid has a catalyst for catalytic oxidation and an electron acceptor, but the catalyst needs a noble metal bipyridyl ruthenium as a photosensitizer, so that the further application of the catalyst is limited.
Disclosure of Invention
Aiming at the problems, the invention takes rare earth elements and iron elements as raw materials, prepares a novel non-ruthenium optical drive water oxidation catalyst by the concepts of graphene combination and coordination polymerization, and successfully applies the catalyst to optical drive water oxidation to release oxygen. The catalyst is a novel green catalyst integrating an electron acceptor and a light absorbent, and is expected to be applied to a low-oxygen environment.
The invention provides a preparation method of a catalyst for efficient water oxidation. Graphene oxide is used as an outer membrane, and a stable photosensitive catalyst (PPaba-Fe) with higher activity is successfully synthesized in an aqueous solution by utilizing the binding force between the graphene oxide and p-aminobenzoic acid and the coordination of the p-aminobenzoic acid, Fe (III) and Eu (III) ions2O3/Eu @ GO). This light sensitive catalyst (PPaba-Fe)2O3Eu @ GO) has a size of 400nm and can be used for catalyzing the oxidation of water to produce O2。
The method utilizes graphene oxide to adsorb pi-pi function of p-aminobenzoic acid, then utilizes coordination among carboxyl in p-aminobenzoic acid, iron ions and rare earth ions europium to form iron oxide nano particles, iron ions perform coordination polymerization on aminobenzoic acid to generate polyaniline formic acid, and graphene oxide is coated to form a europium-doped graphene oxide coated polymer nano iron oxide catalyst which can efficiently catalyze the oxidation of water to O2And the chemical property is stable, and the catalyst is easy to recycle, so the prepared catalyst is a novel optical drive water oxidation catalyst integrating a photosensitizer, a catalyst and an electron acceptor.
The invention adopts the following specific technical scheme:
a preparation method of rare earth ion doped graphene oxide coated poly (p-aminobenzoic acid) compound nano iron oxide comprises the following steps:
adding para aminobenzoic acid and sodium hydroxide into an aqueous solution, uniformly mixing the solution by primary magnetic stirring at room temperature, slowly adding the mixed solution into the graphene oxide solution, and performing secondary magnetic stirring; adding ferric chloride solution, and performing magnetic stirring for the third time; then adding europium chloride aqueous solution, and carrying out magnetic stirring for the fourth time. And transferring the final reaction solution into a reaction kettle after stirring for the fourth time, and calcining for 3-12h, preferably 6h at 160 ℃ to obtain the europium-doped graphene oxide coated nano iron oxide catalyst.
Wherein the molar ratio of the p-aminobenzoic acid to the sodium hydroxide is 2:1-1:2, and the optimal molar ratio is 1: 1.
The magnetic stirring time is 30min, and the temperature is room temperature.
Wherein the molar ratio of the para aminobenzoic acid to the ferric chloride is 2:1-1:2, and the optimal molar ratio is 1: 1.
The mass ratio of the graphene oxide to the ferric chloride is 1:13.5-1:30, and the optimal mass ratio is 1: 27.
Wherein the molar ratio of the europium chloride to the ferric chloride is 1:2000-1:5000, and the optimal molar ratio is 1: 2500.
In the preparation method, the graphene oxide is coated on the outer layer while the poly-p-aminobenzoic acid nano iron oxide is synthesized by a one-step hydrothermal method for the first time, so that the electron transfer efficiency of the catalyst is improved. Meanwhile, the doping of rare earth ions is beneficial to improving the energy transfer efficiency of the nano material, and can catalyze the oxidation of water to release oxygen under the condition of no additional substances, so that the function of bionic oxygen release is realized, and the iron-based water oxidation catalyst which is internationally reported for the first time does not use ruthenium as a photosensitizer; in addition, the invention firstly utilizes a one-step hydrothermal method to coat the graphene oxide on the outer layer of the rare earth ion doped nano iron oxide, the nano catalyst improves the electron transfer efficiency by introducing the graphene oxide, improves the energy transfer efficiency of the nano material by doping the rare earth, and obtains a novel catalyst which is formed by coating the rare earth ion doped polymerization nano iron oxide on the outer layer of the graphene oxide, the catalyst has better effect of catalyzing and releasing oxygen on water, and has higher catalytic activity and energy transfer efficiency compared with polymer iron oxide.
Drawings
FIG. 1 shows the preparation of PPaba-Fe in example 12O3(iii) scanning electron micrograph of/Eu @ GO. As can be seen from FIG. 1, PPaba-Fe2O3The particle size of Eu @ GO is uniform, and the rare earth doped nano iron oxide is successfully coated by graphene oxide.
FIG. 2 shows PPaba-Fe under illumination by an LED (4w) lamp2O3Graph of the evolution of oxygen over time as a function of water released by reaction with Eu @ GO (5 mg). As can be seen from the figure, the catalyst can react with water to release oxygen under the irradiation of the LED lamp, and the release amount of the oxygen is gradually increased along with the time in the 2-hour experimental time, which indicates the good water oxidation activity of the catalyst.
Different preparation techniques have an effect on the amount of oxygen released by the catalyst from the water, wherein the catalyst prepared in example 1 has the best activity, and therefore the performance test uses the sample prepared in example 1.
Detailed Description
PPaba-Fe2O3Synthesis of/Eu @ GO
Example 1 (PPaba-Fe)2O3Optimized preparation scheme of Eu @ GO): 1mmol of p-aminobenzoic acid and 1mmol of sodium hydroxide (molar ratio of p-aminobenzoic acid to sodium hydroxide is 1:1) were added to 5mL of the aqueous solution, and the solution was magnetically stirred at room temperature for 30min to mix well. At room temperature, adding a mixed solution of p-aminobenzoic acid and sodium hydroxide into a graphene oxide solution, magnetically stirring for 30min, adding 1mmol of ferric chloride solution into the graphene oxide mixed solution of p-aminobenzoic acid (the volume is 5mL, wherein the molar ratio of ferric chloride to p-aminobenzoic acid is 1:1, and the mass ratio of graphene oxide to ferric chloride is 1:27), magnetically stirring for 30min, adding 0.4 mu mol of europium chloride solution into the mixed solution (the molar ratio of europium chloride to ferric chloride is 1:2500), magnetically stirring for 30min, transferring into a reaction kettle, calcining for 6h at 160 ℃, and obtaining the europium-doped graphene oxide-coated polymer nano-iron oxideAn oxidizing agent.
Example 2: 1mmol of p-aminobenzoic acid and 2mmol of sodium hydroxide (molar ratio of p-aminobenzoic acid to sodium hydroxide is 1:2) were added to 5mL of the aqueous solution, and the solution was stirred magnetically at room temperature for 30min to mix well. At room temperature, adding a mixed solution of p-aminobenzoic acid and sodium hydroxide into a graphene oxide solution, magnetically stirring for 30min, adding 1mmol of ferric chloride solution into the graphene oxide mixed solution of p-aminobenzoic acid (the volume is 5mL, wherein the molar ratio of ferric chloride to p-aminobenzoic acid is 1:1, and the mass ratio of graphene oxide to ferric chloride is 1:27), magnetically stirring for 30min, adding 0.4 mu mol of europium chloride solution into the mixed solution (the molar ratio of europium chloride to ferric chloride is 1:2500), magnetically stirring for 30min, transferring into a reaction kettle, and calcining at 160 ℃ for 6h to obtain the europium-doped graphene oxide-coated polymer nano-iron oxide catalyst.
Example 3: 2mmol of p-aminobenzoic acid and 1mmol of sodium hydroxide (molar ratio of p-aminobenzoic acid to sodium hydroxide is 2:1) were added to 5mL of the aqueous solution, and the solution was stirred magnetically at room temperature for 30min to mix well. At room temperature, adding a mixed solution of p-aminobenzoic acid and sodium hydroxide into a graphene oxide solution, magnetically stirring for 30min, adding 1mmol of ferric chloride solution into the graphene oxide mixed solution of p-aminobenzoic acid (the volume is 5mL, wherein the molar ratio of ferric chloride to p-aminobenzoic acid is 1:2, and the mass ratio of graphene oxide to ferric chloride is 1:27), magnetically stirring for 30min, adding 0.4 mu mol of europium chloride solution into the mixed solution (the molar ratio of europium chloride to ferric chloride is 1:2500), magnetically stirring for 30min, transferring into a reaction kettle, and calcining at 160 ℃ for 12h to obtain the europium-doped graphene oxide-coated polymer nano-iron oxide catalyst.
Example 4: 1mmol of p-aminobenzoic acid and 1mmol of sodium hydroxide (molar ratio of p-aminobenzoic acid to sodium hydroxide is 1:1) were added to 5mL of the aqueous solution, and the solution was magnetically stirred at room temperature for 30min to mix well. At room temperature, adding a mixed solution of p-aminobenzoic acid and sodium hydroxide into a graphene oxide solution, magnetically stirring for 30min, adding 1mmol of ferric chloride solution into the graphene oxide mixed solution of p-aminobenzoic acid (the volume is 5mL, wherein the molar ratio of ferric chloride to p-aminobenzoic acid is 1:1, and the mass ratio of graphene oxide to ferric chloride is 1:15), magnetically stirring for 30min, adding 0.4 mu mol of europium chloride solution into the mixed solution (the molar ratio of europium chloride to ferric chloride is 1:2500), magnetically stirring for 30min, transferring into a reaction kettle, and calcining at 160 ℃ for 6h to obtain the europium-doped graphene oxide-coated polymer nano-iron oxide catalyst.
Example 5: 1mmol of p-aminobenzoic acid and 1mmol of sodium hydroxide (molar ratio of p-aminobenzoic acid to sodium hydroxide is 1:1) were added to 5mL of the aqueous solution, and the solution was magnetically stirred at room temperature for 30min to mix well. At room temperature, adding a mixed solution of p-aminobenzoic acid and sodium hydroxide into a graphene oxide solution, magnetically stirring for 30min, adding 1mmol of ferric chloride solution into the graphene oxide mixed solution of p-aminobenzoic acid (the volume is 5mL, wherein the molar ratio of ferric chloride to p-aminobenzoic acid is 1:1, and the mass ratio of graphene oxide to ferric chloride is 1:27), magnetically stirring for 30min, adding 0.2 mu mol of europium chloride solution into the mixed solution (the molar ratio of europium chloride to ferric chloride is 1:5000), magnetically stirring for 30min, transferring into a reaction kettle, and calcining at 160 ℃ for 3h to obtain the europium-doped graphene oxide-coated polymer nano-iron oxide catalyst.
Example 6: step one, the PPaba-Fe prepared in example 1 was taken2O3Eu @ GO dispersed in 2mL of a PB (pH 8.5) buffer solution at a concentration of 2.5 mg/mL-1And transferring the mixture into a reactor.
Step two, recording O every 10min under the condition of illumination2And (4) releasing the amount.
FIG. 2 shows PPaba-Fe under illumination by an LED (4w) lamp2O3Graph of the evolution of oxygen over time as a function of water released by reaction with Eu @ GO (5 mg). As can be seen from the figure, the catalyst can react with water to release oxygen under the irradiation of the LED lamp, and the release amount of the oxygen is gradually increased along with the time in the 2-hour experimental time, which indicates the good water oxidation activity of the catalyst.
Claims (6)
1. The water oxidation catalyst is characterized in that the water oxidation catalyst is a nano iron oxide catalyst coated by europium-doped graphene oxide, and the nano iron oxide catalyst is prepared by one-step hydrothermal processThe outer layer is coated with graphene oxide while the poly-p-aminobenzoic acid nano iron oxide is synthesized by the method, and the size of the water oxidation catalyst is 400nm, so that the catalyst can be used for catalyzing water oxidation to generate O2The optical drive water oxidation catalyst integrates a photosensitizer, a catalyst and an electron acceptor.
2. The method for preparing a water oxidation catalyst according to claim 1, comprising the following steps: adding para aminobenzoic acid and sodium hydroxide into an aqueous solution, uniformly mixing the solution by primary magnetic stirring at room temperature, slowly adding the mixed solution into the graphene oxide solution, and performing secondary magnetic stirring; adding ferric chloride solution, and performing magnetic stirring for the third time; then adding europium chloride aqueous solution, and performing magnetic stirring for the fourth time; and transferring the final reaction solution into a reaction kettle after stirring for the fourth time, and calcining for 3-12h at 160 ℃ to obtain the europium-doped graphene oxide coated nano iron oxide catalyst.
3. The method of claim 2, wherein the molar ratio of p-aminobenzoic acid to sodium hydroxide is from 2:1 to 1: 2; the molar ratio of the para aminobenzoic acid to the ferric chloride is 2:1-1: 2; the mass ratio of the graphene oxide to the ferric chloride is 1:13.5-1: 30; the molar ratio of the europium chloride to the ferric chloride is 1:2000-1: 5000.
4. The method of claim 3, wherein the molar ratio of p-aminobenzoic acid to sodium hydroxide is 1: 1; the molar ratio of the para aminobenzoic acid to the ferric chloride is 1: 1; the mass ratio of the graphene oxide to the ferric chloride is 1: 27; the molar ratio of the europium chloride to the ferric chloride is 1: 2500.
5. The method of claim 2, wherein the magnetic stirring is performed for 30min at room temperature.
6. The method of claim 2, wherein the calcining is carried out at 160 ℃ for 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910118208.6A CN109821573B (en) | 2019-02-15 | 2019-02-15 | A kind of water oxidation catalyst and preparation method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910118208.6A CN109821573B (en) | 2019-02-15 | 2019-02-15 | A kind of water oxidation catalyst and preparation method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109821573A CN109821573A (en) | 2019-05-31 |
| CN109821573B true CN109821573B (en) | 2022-02-15 |
Family
ID=66862093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910118208.6A Active CN109821573B (en) | 2019-02-15 | 2019-02-15 | A kind of water oxidation catalyst and preparation method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109821573B (en) |
Citations (3)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8822367B2 (en) * | 2009-03-17 | 2014-09-02 | Emory University | Polyoxometalate water oxidation catalysts and methods of use thereof |
-
2019
- 2019-02-15 CN CN201910118208.6A patent/CN109821573B/en active Active
Patent Citations (3)
| 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 |
| 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 |
|---|
| Polymer United Fe2O3 Nanospheroids for Water Oxidation and the Green Synthesis of 2,3-Dihydrophthalazine-1,4-dione;Dong-liang Huang等;《ACS Sustainable Chem. Eng.》;20180720;第6卷;11280-11285 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109821573A (en) | 2019-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kumar et al. | Noble metal-free metal-organic framework-derived onion slice-type hollow cobalt sulfide nanostructures: Enhanced activity of CdS for improving photocatalytic hydrogen production | |
| CN111389442B (en) | P-N heterojunction composite material loaded on surface of foamed nickel and preparation method and application thereof | |
| CN107175112B (en) | A kind of micromotor photocatalyst and its preparation method and application | |
| CN104445508B (en) | The economic benefits and social benefits light Fenton denitrogenation method of Manganese Ferrite or its carbon composite | |
| CN104923276B (en) | A kind of preparation method of the compound nickel ferrite based magnetic loaded magnetic photocatalytic material of graphite type carbon nitride | |
| CN107008467B (en) | Preparation method and application of heterojunction photocatalyst | |
| CN106252675A (en) | A kind of CuO NiO/rGO composite possessing efficient electric catalytic oxidation-reduction performance | |
| CN104941671A (en) | Zinc ferrite/bismuth oxyiodide magnetic composite visible photocatalyst and preparation method thereof | |
| JP3586242B2 (en) | Method for producing cadmium sulfide-based photocatalyst for hydrogen generation and method for producing hydrogen thereby | |
| CN106654304A (en) | CuO/rGO composite material having efficient electrocatalysis oxygen reducing performance | |
| CN106975499B (en) | Ag @ AgCl/rGO sandwich nanocomposite and preparation method and application thereof | |
| CN109821573B (en) | A kind of water oxidation catalyst and preparation method and use | |
| CN102921438B (en) | Preparation for silver phosphate nano ball-graphene composite material and photocatalysis application | |
| CN113117696A (en) | Cadmium sulfide-based composite photocatalytic material and preparation method and application thereof | |
| CN110586137B (en) | Containing Mn0.5Cd0.5Preparation method of S and Au supported photocatalyst | |
| CN108295903A (en) | A kind of cadmiumsulfide quantum dot-phthalein mountain valley with clumps of trees and bamboo bronzing catalyst and preparation method for hydrogen manufacturing | |
| CN112675862A (en) | Preparation method of metal phthalocyanine modified zinc oxide catalyst | |
| Jiang et al. | A highly dispersed magnetic polymetallic catalyst to activate peroxymonosulfate for the degradation of organic pollutants in wastewater | |
| CN117299140A (en) | Preparation method and application of photocatalytic materials with controllable internal stress and unsaturation | |
| CN113976158B (en) | A self-doped nitrogen porous carbon catalyst supporting cobalt oxide and its preparation method and application | |
| CN114177911B (en) | Carbon-supported multi-metal oxide catalyst and preparation method and application thereof | |
| CN114377696A (en) | Biomembrane-based BiOClxBr(1-x)/Au/MnO2Composite material and preparation method and application thereof | |
| CN109908921B (en) | MoS2NiO blankCore microsphere material, preparation method and application | |
| CN112657514A (en) | Photocatalyst filled with porous nano ZnS @ ZnO hollow spheres and preparation method thereof | |
| CN111359630A (en) | Composite material and preparation method thereof |
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 |