CN108325529B - Photocatalytic water oxidation catalyst and preparation method thereof - Google Patents
Photocatalytic water oxidation catalyst and preparation method thereof Download PDFInfo
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- B01J35/39—
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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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a photocatalytic water oxidationThe catalyst and the preparation method thereof are used for photocatalytic water oxidation reaction. The preparation method comprises the following steps: firstly, different precursor Co nano particles are prepared through hydrothermal reaction, and the Co nano particles generate Co @ Co in situ under the conditions of strong oxidizing property and strong alkalinity3O4A water oxidation catalyst. The catalyst can catalyze water to oxidize to generate oxygen in an alkaline solution with an oxidant under the irradiation of visible light.
Description
Technical Field
Different cobalt salts are used as cobalt sources, different reducing agents and surfactants are added, and different Co nanoparticles are prepared at high temperature and high pressure. Then taking Co nano-particles as a precursor, and preparing Co @ Co in situ in an alkaline solution dissolved with an oxidant3O4Has good catalytic performance and can be used as a photocatalytic water oxidizer.
Background
The problems of exhaustion of fossil energy and environmental pollution become two major problems which need to be solved urgently in the world today. Solar energy is widely and cleanly renewable, so that the solar energy is attracted by people, and is converted into clean chemical energy by artificially simulating photosynthesis of plants, and the method is a research hotspot for developing new energy at present. Wherein the catalytic water splitting by solar energy comprises two half reactions: the water is reduced to produce hydrogen and the water is oxidized to produce oxygen. The key to the realization of the full decomposition of water is that the water oxidation reaction has a high reaction barrier, so that designing and synthesizing a high-efficiency water oxidation catalyst and using the high-efficiency water oxidation catalyst in water oxidation catalysis under visible light are effective means for solving the problems.
In the 70's of the 20 th century, the photocatalytic water splitting was first discovered and proposed using photocatalysts. For semiconductor photocatalysts, the basic principle of photocatalytic reaction is that after being excited by photons with energy larger than the band gap energy of the photocatalyst, electrons and holes are separated and respectively transmitted to the surface of a semiconductor, and the photocatalyst and surface water molecules undergo oxidation-reduction reactions at positions of a conduction band and a valence band, wherein the electrons and the surface water molecules undergo reduction reactions to generate hydrogen, and the holes and the water molecules undergo oxidation reactions to generate oxygen, so that photocatalytic water decomposition is realized. In recent years, semiconductor photocatalytic water oxidizers have rapidly developed, among which cobalt-based semiconductor lightThe catalytic material attracts more and more scientists' attention due to its abundant resources, low price and easy availability, for example: kazuhiko Maeda and his team research found that cobalt oxide nanoclusters loaded on rutile titanium dioxide have dual effects of water oxidation catalysis and visible light absorption (ACS applied materials)&Interfaces, 9 (2017) 6114-6122.). His research team also demonstrated and reported that cobalt hydroxide nanoclusters modified with wider forbidden bandwidth oxide semiconductors had good ability to catalyze water oxidation with a maximum oxygen production rate of 110 μmol h-1g-1(Angewandte Chemie International Edition, 55 (2016) 8309-. Fang et al demonstrated CoOxModified CeO2The hollow structure has good photocatalytic water oxidation performance under visible light, and the average oxygen production rate reaches 208.4 mu mol h-1g-1(Dalton transactions, 46 (2017) 10578-. Recent work in our laboratory also found and demonstrated that in situ generated Co @ CoO exhibited excellent activity when used as a water oxidation catalyst (Applied Catalysis B: Environmental, 210 (2017) 67-76). Reported documents show that the oxygen generation efficiency and the oxygen generation rate of the cobalt-based semiconductor water oxidation catalyst are still low, and the preparation method is not simple enough, so that the cobalt-based catalyst with simplicity and high efficiency is needed to be further developed.
The invention synthesizes Co nano-particles as a precursor through solvothermal reaction, and generates Co @ Co in situ under the conditions of an oxidant and an alkaline solution3O4The water oxidation catalyst is used for carrying out photocatalytic water oxidation test on the system under the condition of not needing additional treatment, namely Co @ Co3O4The catalyst shows excellent photocatalytic water oxidation performance, and the average oxygen production rate reaches 2778 mu mol h-1g-1After four times of circulation use, the catalytic activity can still keep 94.7 percent of the initial activity.
Disclosure of Invention
The invention aims to improve the efficiency and the capability of water oxidation reaction, and provides a simple preparation method of a Co-based semiconductor catalyst3O4The water oxidation catalyst realizes high-efficiency photocatalytic water oxidation under visible light in an alkaline solution containing an oxidant. The operation steps are as follows:
(1) cobalt acetate (Co (CH)3COO)2·4H2O), cobalt nitrate (Co (NO)3)2·6H2O), cobalt sulfate (CoSO)4·7H2O), cobalt chloride (CoCl)2·6H2O) and surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), polyvinylpyrrolidone (PVP) or Sodium Dodecyl Benzene Sulfonate (SDBS) are dispersed in different solvents, different reducing agents are added for reduction, and different Co nanoparticle precursors are generated by hydrothermal treatment after full reaction.
(2) Dispersing prepared Co nanoparticles (1-10 mg) in sodium persulfate (Na) dissolved with certain amount of oxidant2S2O8) Potassium persulfate (K)2S2O8) Potassium monopersulfate (2 KHSO)5·KHSO4·K2SO4) (5-200 mg) in an alkaline solution, wherein the volume of the alkaline solution is 10-100 mL, and the catalyst Co @ Co is generated in situ3O4。
(3) In which a certain amount of Co @ Co is dispersed3O4In the alkaline solution system of the catalyst and the oxidant, the high-efficiency photocatalytic water oxidation can be realized by illuminating the catalyst and the oxidant.
Drawings
FIG. 1 shows Co nanoparticles and Co @ Co3O4PXRD diffraction pattern of the photocatalyst;
FIG. 2 is Co @ Co3O4SEM image of photocatalyst;
FIG. 3 is Co @ Co3O4High resolution transmission electron micrographs (HR-TEM) of the photocatalyst;
FIG. 4 is Co @ Co3O4Co2p high power XPS spectra of the photocatalyst;
FIG. 5 is Co @ Co3O4A uv-visible diffuse reflectance spectrum of the photocatalyst;
FIG. 6 is Co @ Co3O4A photocatalyst photocurrent-time spectrum;
FIG. 7 is Co @ Co3O4The performance diagram of the photocatalyst for catalyzing water decomposition to generate oxygen.
Detailed Description
The invention will be further illustrated by the following specific examples.
Example 1: preparation of Co nanoparticles:
the synthesis process of the precursor comprises the following steps: 0.498 g (2 mmol) of cobalt acetate (Co (CH) was weighed out3COO)2·4H2O) and 0.5 g (1.37 mmol) of cetyltrimethylammonium bromide (CTAB), dispersing the mixture in 30 mL of ethylene glycol solution, stirring the mixture to dissolve the mixture, after stirring the mixture uniformly, dropwise adding 2 mL (excessive) of 80% hydrazine hydrate into the beaker at the speed of 2 drops/s, and stirring the mixture for 1 hour after the dropwise addition is finished. And transferring the mixed solution into a 50mL reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into a 180 ℃ oven for heat preservation for 6 hours. After the reaction is completed, the reaction kettle is taken out, cooled by water and poured out. Washing the precipitate with distilled water and absolute ethyl alcohol respectively for 3 times to obtain pure cobalt simple substance, and drying in a vacuum drying oven at 40 ℃ for 12 h to obtain grey black Co simple substance.
Example 2: preparation of Co nanoparticles:
0.48 g of cobalt chloride (CoCl) was added in distilled water as a solvent2·6H2O) and 1.2 g of sodium hydroxide were dissolved in 50mL of distilled water and magnetically stirred for 10 min. Then adding 1 mL of ethylenediamine and 1 mL of hydrazine hydrate, magnetically stirring for 15 min, transferring the mixed solution into a 100mL of polytetrafluoroethylene-lined high-pressure reaction kettle, and placing the reaction kettle into a 200 ℃ oven for heat preservation for 4 h. And after the reaction is finished, naturally cooling to room temperature, filtering the obtained black precipitate, washing the black precipitate for 3 times by using distilled water and alcohol respectively, and performing vacuum drying at 50 ℃ for 3 hours to obtain black Co powder.
Example 3: preparation of Co nanoparticles:
adding 10 mmol of cobalt nitrate (Co (NO)3)2·6H2O) and 10 mmol of polyvinylpyrrolidone (PVP) are dissolved in 40 mL of ethylene glycol and uniformly dispersed by magnetic stirring and ultrasonic. To the suspension was added dropwise 4 mL of anhydrous ethylenediamine with stirring. Stirring for half an hour, transferring the mixed solution to 50The reaction kettle with the mL polytetrafluoroethylene lining is hermetically placed in a reactor with 200 mL polytetrafluoroethylene liningoC, reacting for 12 hours in an oven. Naturally cooling to room temperature, separating with magnetic field, washing with distilled water and anhydrous ethanol for several times, 60%oAnd C, vacuum drying for 12 h to obtain gray Co powder.
Example 4: preparation of Co nanoparticles:
weighing 15 mL of a small amount of PVP (polyvinyl pyrrolidone) surfactant and 5% NaOH solution in mass fraction into 20 mL of hydrazine hydrate, and uniformly dispersing by ultrasonic; 0.7 g of cobalt chloride (CoCl) was weighed out2·6H2O) is dissolved in 20 mL of absolute ethyl alcohol, the mixture is stirred uniformly and then is dripped into a big beaker filled with hydrazine hydrate at the speed of 30d/min, and a large amount of bubbles are generated in the reaction along with the generation of black Co particles. And centrifuging to take out Co particles, washing the Co particles for a plurality of times by using distilled water and ethanol, and storing the prepared sample in normal hexane.
Example 5: preparation of Co nanoparticles:
50 mmol of cobalt sulfate (CoSO) were weighed4·7H2O) and 15 mmol Sodium Dodecylbenzenesulfonate (SDBS) were dispersed in 60 mL distilled water, and 0.4 mol sodium hypophosphite (NaH) was added2PO2·H2O), uniformly stirring, completely reacting, and then loading into a kettle 110oAnd C, preserving the heat for 24 hours. Naturally cooling to room temperature, washing with distilled water and ethanol for several times, and washing with water and ethanol for 60 daysoAnd C, vacuum drying for 4 h to obtain black and gray Co nanoparticles.
Example 6: preparation of Co nanoparticles:
2 mmol of cobalt chloride (CoCl)2·6H2O), 10 mmol of sodium hypophosphite (NaH)2PO2·H2O) and 10 mmol of trisodium citrate are dissolved in 40 mL of distilled water and dispersed evenly, 10mL of NaOH solution with the concentration of 10 mol/L is added into the mixed solution, the mixture is stirred for half an hour to ensure that the reaction is complete, the mixture is transferred into a reaction kettle, 160oAnd C, preserving the heat for 20 hours. Washing with distilled water and absolute ethyl alcohol for several times to finally prepare the black Co nano particles.
Example 7: co @ Co3O4In situ generation of photocatalyst and for photocatalytic water oxidation:
Co@Co3O4in situ generation and photocatalysisThe chemical process is as follows: weighing 1mg of precursor Co nano-particles and 10mg of oxidant sodium persulfate (Na) dissolved in the precursor Co nano-particles2S2O8) Stirring the 10mL NaOH solution with the pH value of 10 for 1-3 minutes to obtain Co @ Co3O4Then, the oxygen is obtained by giving light.
Example 8: co @ Co3O4In situ generation of photocatalyst and for photocatalytic water oxidation:
Co@Co3O4the in-situ generation and photocatalysis process is as follows: weighing 2mg of precursor Co nano-particles and 20mg of potassium persulfate (K) dissolved with oxidant2S2O8) Stirring the 10mL KOH solution with the pH value of 12 for 1 to 3 minutes to obtain Co @ Co3O4Then, the oxygen is obtained by giving light.
Example 9: co @ Co3O4In situ generation of photocatalyst and for photocatalytic water oxidation:
Co@Co3O4the in-situ generation and photocatalysis process is as follows: weighing 10mg of precursor Co nano-particles and 50mg of oxidant sodium persulfate (Na) dissolved in the precursor Co nano-particles2S2O8) Stirring the solution in 50mL of NaOH solution with pH of 13 for 1-3 minutes to obtain Co @ Co3O4Then, the oxygen is obtained by giving light.
Example 10: co @ Co3O4In situ generation of photocatalyst and for photocatalytic water oxidation:
Co@Co3O4the in-situ generation and photocatalysis process is as follows: weighing 20mg of precursor Co nano-particles and 100mg of potassium monopersulfate (2 KHSO) dissolved with oxidant5·KHSO4·K2SO4) Stirring the 100mL KOH solution with the pH value of 14 for 1 to 3 minutes to obtain Co @ Co3O4Then, the oxygen is obtained by giving light.
Example 11: co @ Co3O4In situ generation of photocatalyst and for photocatalytic water oxidation:
Co@Co3O4the in-situ generation and photocatalysis process is as follows: weighing 50mg of precursor Co nano particles and 100mg of oxygen dissolved in the precursor Co nano particlesPotassium monopersulfate (2 KHSO) as the oxidant5·KHSO4·K2SO4) Stirring the 100mL of NaOH solution with the pH value of 12 for 1-3 minutes to obtain Co @ Co3O4Then, the oxygen is obtained by giving light.
Example 12: co @ Co3O4In situ generation of photocatalyst and for photocatalytic water oxidation:
Co@Co3O4the in-situ generation and photocatalysis process is as follows: weighing 20mg of precursor Co nano-particles and potassium persulfate (K) dissolved with 200mg of oxidant2S2O8) Stirring the 100mL of KOH solution with the pH value of 13 for 1 to 3 minutes to obtain Co @ Co3O4Then, the oxygen is obtained by giving light.
Claims (2)
1. Co @ Co3O4The preparation method comprises the following steps:
preparation of Co nanoparticles
Taking different cobalt salts as cobalt sources, adding different reducing agents and surfactants, and preparing Co nanoparticles in different solvents at high temperature and high pressure;
(di) Co @ Co3O4The preparation method comprises any one of the following methods:
(1) weighing 1mg of precursor Co nanoparticles and 10mg of oxidant sodium persulfate (Na) dissolved in the precursor Co nanoparticles2S2O8) Stirring the 10 mLNaOH solution with the pH of 10 for 1 to 3 minutes to obtain Co @ Co3O4；
(2) Weighing 2mg of precursor Co nano-particles and 20mg of potassium persulfate (K) dissolved with oxidant2S2O8) Stirring the 10 mLKOH solution with the pH value of 12 for 1 to 3 minutes to obtain Co @ Co3O4；
(3) Weighing 10mg of precursor Co nano-particles and 50mg of oxidant sodium persulfate (Na) dissolved in the precursor Co nano-particles2S2O8) Stirring the solution in 50mL of NaOH solution with pH of 13 for 1-3 minutes to obtain Co @ Co3O4；
(4) Weighing precursor Co nano-particles20mg of pellets and 100mg of potassium monopersulfate (2 KHSO) as an oxidizing agent dissolved therein5·KHSO4·K2SO4) Stirring the 100mL KOH solution with the pH value of 14 for 1 to 3 minutes to obtain Co @ Co3O4；
(5) Weighing 50mg of precursor Co nano-particles and 100mg of potassium monopersulfate (2 KHSO) dissolved with oxidant5·KHSO4·K2SO4) Stirring the 100mL of NaOH solution with the pH value of 12 for 1-3 minutes to obtain Co @ Co3O4；
(6) Weighing 20mg of precursor Co nano-particles and potassium persulfate (K) dissolved with 200mg of oxidant2S2O8) Stirring the KOH solution with the pH of 13 of 100ml for 1 to 3 minutes to obtain Co @ Co3O4。
2. The method of claim 1, wherein: with cobalt acetate (Co (CH)3COO)2·4H2O), cobalt nitrate (Co (NO)3)2·6H2O), cobalt sulfate (CoSO)4·7H2O), cobalt chloride (CoCl)2·6H2O) as cobalt source, hydrazine hydrate, ethylenediamine, sodium hypophosphite (NaH)2PO2·H2O) is used as a providing body of a reducing agent, and Cetyl Trimethyl Ammonium Bromide (CTAB), polyvinylpyrrolidone (PVP) and Sodium Dodecyl Benzene Sulfonate (SDBS) are used as providing agents of a surfactant.
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