CN113941337A - Strong magnetic cerium, potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst and preparation method and application thereof - Google Patents
Strong magnetic cerium, potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst and preparation method and application thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000001257 hydrogen Substances 0.000 title claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 27
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 21
- 239000006104 solid solution Substances 0.000 title claims abstract description 21
- YPQJHZKJHIBJAP-UHFFFAOYSA-N [K].[Bi] Chemical compound [K].[Bi] YPQJHZKJHIBJAP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 10
- 239000011975 tartaric acid Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 9
- 230000005294 ferromagnetic effect Effects 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 7
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- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 229910002902 BiFeO3 Inorganic materials 0.000 description 10
- 230000004044 response Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910001451 bismuth ion Inorganic materials 0.000 description 3
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 3
- 229960000623 carbamazepine Drugs 0.000 description 3
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- 229960003405 ciprofloxacin Drugs 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960001259 diclofenac Drugs 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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Abstract
The invention belongs to the fields of inorganic chemistry, energy technology and catalysis, and particularly relates to a strong magnetic cerium and potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst, and a preparation method and application thereof. The preparation method of the piezoelectric hydrogen production catalyst comprises the following steps: mixing a mixture containing a Fe source, a Bi source, a K source and a Ce source with ethylene glycol to obtain a mixed solution; then adding tartaric acid, continuously stirring in a heating state until the tartaric acid is completely dissolved to form gel, and drying the gel to obtain a CKBF precursor; calcining the obtained CKBF precursor to obtain the CKBFA piezoelectric hydrogen production catalyst. The preparation method of the strong magnetic cerium, potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst provided by the invention is simple in process, and the prepared material is good in thermal stability and high in catalytic activity, and compared with BiFeO prepared by the traditional method3Has strong magnetism, is easier to recycle and has stronger hydrogen production effect.
Description
Technical Field
The invention belongs to the fields of inorganic chemistry, energy technology and catalysis, and particularly relates to a strong magnetic cerium and potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst, and a preparation method and application thereof.
Background
At present, with the continuous consumption of fossil energy, the demand of people for clean energy is continuously increasing. The hydrogen energy is known as the most promising clean energy in the 21 st century, and the effective utilization of the hydrogen energy can effectively alleviate the problems of environmental pollution and energy consumption. Generally, hydrogen can be directly prepared by decomposing water through sunlight, but the problems of no response in darkness, low sunlight utilization rate and the like become limiting conditions for the development of photocatalytic hydrogen production technology. In addition, the water electrolysis technology is also a hot topic of hydrogen production in recent years, however, the large consumption of electric energy also becomes a significant defect of the technology. Therefore, the invention of a simple and efficient hydrogen production technology is urgent.
In recent years, multiferroic materials have received much attention because they have multiple properties at the same time. BiFeO, a classic multiferroic material with both ferroelectric and ferromagnetic properties3Under the action of stress, local dipole moment of the material is polarized, and potential difference is generated inside the material to form a polarized electric field, so that mechanical energy is converted into electric energy, namely the piezoelectric effect. The piezoelectric electric field can promote the migration of free electrons on the material to cause the separation of electron holes, and the separated charges can quickly and efficiently decompose water, so that the piezoelectric electric field has great potential in the field of hydrogen production. Typically, BiFeO3The piezoelectricity of the composite material mainly comes from the fact that ferroelectric polarization along the (111) direction is formed by hybridization between 6s lone pair electrons of the A-site bismuth ions and 2p orbitals of oxygen atoms, but due to the fact that bismuth element can be partially volatilized in the high-temperature sintering process, the appearance of mixed phases and leakage current is caused, and the piezoelectric performance is affected; the substitution of the A site of the equivalent element can effectively improve the crystallinity of the material and reduce the leakage current, thereby improving the piezoelectric property. Meanwhile, BiFeO3The magnetism comes from residual magnetic moment generated by spin arrangement of B-site iron ions, but the spin is inclined at a small angle and forms a periodic helical structure as long as 62nm, the macroscopic net magnetic moment of the material is counteracted by the structure, although the substitution of B-site element can inhibit the periodic helical structure to a certain extent, the crystallinity cannot be improved, and even impurities are broughtAnd (4) phase(s). Therefore, the improvement of both piezoelectric performance and magnetic response on the basis of the improvement of the crystalline phase of the material is a key problem to be solved at present.
Disclosure of Invention
The invention aims to provide a preparation method of a strong magnetic cerium and potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst. The method is simple and easy to implement, and the obtained hydrogen production catalyst has strong magnetism and is easy to recover, thereby providing a powerful basis for industrial application.
The invention also aims to provide the ferromagnetic cerium and potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst prepared by the method. The hydrogen production catalyst is changed to use ultrasound as a piezoelectric driving force, and after 80min of ultrasound, the hydrogen production amount can reach 515 mu mol/g which is far higher than 274 mu mol/g of undoped bismuth titanate.
The invention further aims to provide the application of the ferromagnetic cerium and potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst in the field of hydrogen production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a strong magnetic cerium, potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst specifically comprises the following steps:
step 1: weighing Fe (NO)3)3·9H2O，Bi(NO3)2·5H2O，KNO3And Ce (NO)3)3·6H2O, mixing with ethylene glycol to obtain a mixed solution;
step 2: adding tartaric acid into the mixed solution obtained in the step 1, continuously stirring the mixed solution in a heating state until the tartaric acid is completely dissolved to form gel, and drying the gel to obtain a CKBF precursor;
and step 3: calcining the obtained CKBF precursor to obtain the CKBF piezoelectric hydrogen production catalyst;
Fe (NO) as described in step 13)3·9H2The molar volume ratio of O to ethylene glycol is 0.01 mol: 20-50 mL, preferably 0.01 mol: 40 mL.
In the step 2, the heating temperature is 70-90 ℃, and the stirring time is 1-3 hours.
The amount of tartaric acid in step 2 is the same as the sum of the amounts of heavy metal cation substances in step 1, and the sum of the amounts of the heavy metal cation substances is Fe (NO)3)3·9H2O，Bi(NO3)2·5H2O，KNO3And Ce (NO)3)3·6H2Sum of the amounts of substances of O.
In the step 2, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
And 3, calcining at 500-600 ℃ for 1-3 h. Preferably, the temperature rise program during the calcination is set to be 5-15 ℃/min.
And 3, calcining the CKBF precursor, preferably naturally cooling, washing with ethanol and water for several times, and drying to obtain the final CKBF piezoelectric hydrogen production catalyst.
The strong magnetic cerium, potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst is prepared by the method, and the chemical formula of the catalyst is CexKyBi(1-x-y)FeO3(CKBF)，0.05≤x≤0.2，0.05≤y≤0.2。
The strong magnetic cerium and potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst is applied to the field of hydrogen production.
The A position is replaced by the A position of an aliovalent element, the crystallinity and the structural distortion of the material are enhanced, the piezoelectric response is improved, and the valence state compensation of the B position element can be caused, so that the valence state of the B position element is changed, and the aim of enhancing ferromagnetism is fulfilled; meanwhile, the multi-element formed by multiple elements easily causes the appearance of solid solution state structures with different end materials in the system, and the appearance of the solid solution not only can inhibit the generation of heterogeneous phases, but also can construct a homomorphic phase boundary and improve the piezoelectric performance. Aiming at the key problems existing in the prior art and the characteristic of A-site doping, the invention adopts the simultaneous introduction of equivalence (Ce) on the A site3+) And aliovalent (K)+) Element partially replaces the original Bi3+Thus being BiFeO3The high-efficiency hydrogen production and the simple recovery of the base piezoelectric material provide feasible bases. Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a preparation method of a strong magnetic cerium and potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst. On one hand, rare earth metal Ce with equal valence and good thermal stability is selected3+The bismuth ion at the A position is replaced, the crystallinity of the material is improved, the structural symmetry is damaged, the structural distortion is enhanced, and the material is easier to generate a polarization electric field under the driving of pressure, so that the piezoelectric hydrogen production effect is improved. On the other hand, selecting alkali metals K with different valence states+Bismuth ions in A position are replaced, valence change of iron ions is initiated, magnetic response is increased, and solid solution form can be initiated by the existence of multiple elements and multiple components, so that miscellaneous items are inhibited from being generated, a homomorphic phase boundary is constructed, and piezoelectric performance is improved. The method comprises the steps of chemically fusing raw materials in a proper proportion, adding tartaric acid as a chelating agent, heating to form gel, drying, grinding and calcining at high temperature to obtain a sample, and successfully preparing BiFeO3Two elements of Ce and K are introduced, so that the aims of simultaneously improving the crystal phase structure, increasing the piezoelectric property and improving the magnetic response are fulfilled, and the method has great significance for popularizing the piezoelectric hydrogen production technology in industrial application.
Drawings
In FIG. 1: (a) BiFeO prepared in embodiment 1 of the invention3And an X-ray diffraction pattern of CKBF; (b) is a scanning electron micrograph of CKBF-10% prepared in embodiment 1 of the present invention.
FIG. 2 is a microscope image of the piezoelectric response stress of CKBF-10% prepared in embodiment 1 of the present invention
FIG. 3 shows a magnetic loop for preparing CKBF-10% in accordance with embodiment 1 of the present invention.
FIG. 4 shows BiFeO prepared in embodiment 1 of the present invention3And piezoelectric hydrogen production performance diagram of CKBF.
FIG. 5 shows BiFeO prepared in embodiment 1 of the present invention3KBF-10%, CBF-10% and CKBF-10%.
Fig. 6 shows that hydrogen production and pollutant degradation are simultaneously achieved by using 10% of CKBF prepared in embodiment 1 of the present invention.
FIG. 7 shows BiFeO prepared in embodiment 1 of the present invention3And CKBF-10% piezoelectric response current versus time plot.
FIG. 8 is a graph (a) of the performance of recycling hydrogen production of CKBF-10% prepared in embodiment 1 of the present invention and a schematic diagram (b) of magnetic separation recovery.
Detailed Description
The present invention is further described with reference to the accompanying drawings, and the following examples are only for clearly illustrating the technical solutions of the present invention, and should not be taken as limiting the scope of the present invention.
Example 1
The preparation method comprises the following specific steps:
step 1: 0.007 to 0.01mol of Bi (NO) is weighed out respectively3)2·5H2O, 0-0.0015mol KNO3And 0 to 0.0015mol of Ce (NO)3)3·6H2Adding O into a conical flask containing 40mL of glycol, respectively accounting for 70% -100%, 0-15% and 0-15% of Bi, K and Ce, and uniformly stirring. Then 0.01mol of Fe (NO) is weighed out3)3·9H2Adding O into the above mixed solution, and stirring until the solid is completely dissolved to obtain clear brownA red solution.
Step 2: adding 3.002g of tartaric acid into the brownish red clear solution obtained in the step 1, then transferring the conical flask into a constant-temperature water bath kettle, stirring the solution in the water bath at the temperature of 80 ℃ for 2 hours, transferring the obtained gel into a watch glass, drying the gel at the temperature of 70 ℃ overnight to form xerogel solid, and then grinding the xerogel solid to obtain CKBF precursor powder. And calcining the CKBF precursor powder at 550 ℃ for 2h to obtain CKBF solid.
Control of Bi (NO)3)2·5H2The addition amount of O is 0.01mol, KNO3And Ce (NO)3)3·6H2The adding amount of O is 0mol, and the obtained CKBF is recorded as BiFeO3(ii) a Control of Bi (NO)3)2·5H2The addition of O is 0.09mol, KNO3And Ce (NO)3)3·6H2The amount of O added was 0.005mol, respectively, and the CKBF thus obtained was recorded as Ce0.05K0.05Bi0.9FeO3(CKBF-5%); control of Bi (NO)3)2·5H2The addition of O is 0.08mol, KNO3And Ce (NO)3)3·6H2The addition of O is 0.01mol respectively, and the obtained CKBF is recorded as Ce0.1K0.1Bi0.8FeO3(CKBF-10%); control of Bi (NO)3)2·5H2The addition of O is 0.07mol, KNO3And Ce (NO)3)3·6H2The addition of O is 0.015mol respectively, and the CKBF is recorded as Ce0.15K0.15Bi0.7FeO3(CKBF-15%). Control of Bi (NO)3)2·5H2The addition of O is 0.09mol, KNO3Is added in an amount of 0mol, Ce (NO)3)3·6H2The adding amount of O is 0.01mol, and the obtained CKBF is recorded as CBF-10%; control of Bi (NO)3)2·5H2The addition of O is 0.09mol, KNO3Is added in an amount of 0.01mol, Ce (NO)3)3·6H2The amount of O added was 0mol and the CKBF obtained was recorded as KBF-10%.
FIG. 1(a) is an X-ray diffraction pattern of the piezoelectric hydrogen production catalyst prepared in the embodiment 1 of the present invention, from which BiFe prepared is observedO3The standard card number JCPDS No.14-0181 is well matched, and no additional peak is added when two elements including Ce and K are added, which means that a solid solution is formed. Fig. 1(b) is a scanning electron micrograph of 10% of the CKBF-prepared in embodiment 1 of the present invention, and it is seen from the micrograph that the morphology of 10% of the prepared CKBF-is irregular particles. Fig. 2 is a microscope image of the piezoelectric response of CKBF-10%, from which it is seen that the saturated phase voltage loop exhibits significant hysteresis and 180 ° phase switching, and the amplitude voltage hysteresis loop exhibits a similar "butterfly" appearance, which is well documented as the excellent piezoelectric properties of CKBF-10%. FIG. 3 is a graph of the magnetic force of CKBF-10% prepared according to the present invention, in which it is seen that the magnetization value of CKBF-10% in a saturated state is about 6.3378emu/g, indicating that CKBF-10% has excellent magnetic properties.
Example 2
5mg of piezoelectric hydrogen production catalysts of different Ce and K doping contents prepared in example 1 were weighed separately and then transferred to a closed tube containing 5mL of 0.5mol/L sodium sulfite solution, and nitrogen was passed through for 15 minutes before the reaction to eliminate air interference. Then the reaction solution is transferred to an ultrasonic cleaner with 80W and 40kHz to carry out piezoelectric hydrogen production reaction, samples are taken at certain time, and the production amount of the hydrogen is measured.
FIG. 4 shows the catalyst BiFeO for piezoelectric hydrogen production prepared in embodiment 1 of the present invention3And the piezoelectric hydrogen production performance diagram comprises 5 percent of CKBF, 10 percent of CKBF and 15 percent of CKBF. As is apparent from the graph, the hydrogen production gradually increased with the increase of the reaction time. In addition, CKBF with different Ce and K doping amounts is obviously seen, the piezoelectric hydrogen production effect has obvious optimal value of CKBF-10 percent, and the hydrogen yield reaches 515 mu mol/g after 80 minutes of ultrasonic treatment, which is far higher than BiFeO3274. mu. mol/g.
FIG. 5 shows the piezoelectric hydrogen production catalyst BiFeO prepared in embodiment 1 of the present invention3KBF-10%, CBF-10% and CKBF-10%. As is evident from the figure, the doping of Ce alone and the doping of K alone will yield BiFeO3The hydrogen production performance of the piezoelectric material is respectively improved from 274 mu mol/g to 330 mu mol/g and 314 mu mol/g. WhileThe piezoelectric hydrogen production performance of CKBF-10% is 515 mu mol/g, which is much higher than that of CBF-10% and CKBF-10%, which shows that BiFeO is improved by obvious synergistic effect3The crystal phase structure greatly enhances the piezoelectric hydrogen production performance.
Example 3
5mg of CKBF-10% prepared in embodiment example 1 was weighed into a closed tube, and then 5mL of a contaminant mixture solution (5mg/L carbamazepine, 5mg/L ciprofloxacin, and 5mg/L diclofenac) was added. Nitrogen was passed for 15 minutes before the reaction to exclude interference of hydrogen in air. Then transferred into an ultrasonic cleaner with the frequency of 80W and 40kHz, and aims to use the pollutants as sacrificial agents for piezoelectric hydrogen production so as to realize the simultaneous progress of the piezoelectric hydrogen production reaction and the degradation of the pollutants. Sampling is carried out at certain intervals, the yield of hydrogen is measured, and the removal rate of carbamazepine, ciprofloxacin and diclofenac acid in the solution after the final reaction is detected.
As is apparent from FIG. 6, as the ultrasonic reaction time is prolonged to 80min, the hydrogen production is gradually increased to 334. mu. mol/g, the removal effect of carbamazepine is 62%, the removal rate of ciprofloxacin is 78%, and the removal rate of diclofenac acid reaches 83%. The CKBF-10% can effectively utilize pollutants, the synergistic effect of pollutant degradation and hydrogen production is realized, and the wide application of the CKBF-10% piezoelectric hydrogen production catalyst is well embodied.
Example 4
The specific examples 1 provided a ferromagnetic cerium, potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst CKBF-10% and BiFeO were tested with 0.5mol/L sodium sulfate solution as the conductive solution, platinum wire as the counter electrode, and calomel electrode as the reference electrode3The piezoelectric response current versus time.
FIG. 7 shows that the transient current density of CKBF-10% is much higher than that of BiFeO3. This indicates that the conductivity of the formed CKBF-10% solid solution is much higher than that of pure BiFeO3This is because the introduction of Ce and K destroys BiFeO3The symmetrical structure can generate stronger deformation and stronger polarization under the same piezoelectric force actionThe effect and stronger built-in electric field promote the separation and transfer of carriers.
Example 5
Through the way as shown in fig. 8, the solution after reaction is in a turbid state, but under the action of magnetic force, the solution is quickly clarified, and then the CKBF-10% after use is collected, washed with ethanol and deionized water for several times, and then dried for a recycling experiment, so as to consider the stability of the CKBF-10% piezoelectric hydrogen production performance. As shown in FIG. 8(a), after 4 cycles, the hydrogen production amount by piezoelectric method of CKBF-10% is 515, 499, 490 and 469. mu. mol/g, which well proves the excellent stability and strong magnetism of CKBF-10%, and the schematic diagram of the magnetic separation process is shown in FIG. 8 (b).
The foregoing is only a preferred embodiment of the present invention, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and such modifications and improvements should be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of a strong magnetic cerium, potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst is characterized by comprising the following steps:
step 1: weighing Fe (NO)3)3·9H2O，Bi(NO3)2·5H2O，KNO3And Ce (NO)3)3·6H2O, mixing with ethylene glycol to obtain a mixed solution;
step 2: adding tartaric acid into the mixed solution obtained in the step 1, continuously stirring the mixed solution in a heating state until the tartaric acid is completely dissolved to form gel, and drying the gel to obtain a CKBF precursor;
and step 3: calcining the obtained CKBF precursor to obtain the CKBF piezoelectric hydrogen production catalyst;
step 1 Fe (NO)3)3·9H2O，Bi(NO3)2·5H2O，KNO3And Ce (NO)3)3·6H2The dosage of O satisfies the sum of the dosage of Ce, K and Bi and the dosage of FeThe ratio of the amounts of (1): 1; wherein Bi (NO)3)2·5H2O，KNO3And Ce (NO)3)3·6H2The molar ratios of Bi, K and Ce in the mixture of O are 70-100%, 0-15% and 0-15% respectively.
2. The method of claim 1, wherein: the Bi (NO)3)2·5H2O，KNO3And Ce (NO)3)3·6H2The molar ratio of Bi, K and Ce in the mixture of O is 90-60%, 5-20% and 5-20% respectively.
3. The method of claim 1, wherein: the Bi (NO)3)2·5H2O，KNO3And Ce (NO)3)3·6H2The molar ratios of Bi, K and Ce in the mixture of O are 85-75%, 5-15% and 5-15% respectively.
4. The method of claim 1, wherein:
fe (NO) as described in step 13)3·9H2The molar volume ratio of O to ethylene glycol is 0.01 mol: 20-50 mL.
5. The method of claim 1, wherein: the amount of tartaric acid in step 2 is the same as the sum of the amounts of heavy metal cation substances in step 1, and the sum of the amounts of the heavy metal cation substances is Fe (NO)3)3·9H2O，Bi(NO3)2·5H2O，KNO3And Ce (NO)3)3·6H2Sum of the amounts of substances of O.
6. The method of claim 1, wherein: in the step 2, the heating temperature is 70-90 ℃, and the stirring time is 1-3 hours.
7. The method of claim 1, wherein: and 3, calcining at 500-600 ℃ for 1-3 h.
8. The method of claim 1, wherein: and 3, setting the temperature rise program during calcination to be 5-15 ℃/min.
9. A ferromagnetic cerium, potassium-bismuth ferrite solid solution piezoelectric hydrogen production catalyst is prepared by the method of any one of claims 1 to 8, and has a chemical formula of CexKyBi(1-x-y)FeO3，0.05≤x≤0.2，0.05≤y≤0.2。
10. The piezoelectric hydrogen production catalyst of strong magnetic cerium and potassium-bismuth ferrite solid solution according to claim 9, and application thereof in the field of hydrogen production.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115007164A (en) * | 2022-06-27 | 2022-09-06 | 中山大学 | Preparation of rod-shaped bismuth ferrite piezoelectric catalyst and application of rod-shaped bismuth ferrite piezoelectric catalyst in preparation of hydrogen peroxide and hydrogen by catalytic cracking of water |
| CN116371415A (en) * | 2023-04-14 | 2023-07-04 | 哈尔滨工程大学 | Preparation method of cerium doped material for improving catalytic performance of bismuth ferrite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170157A (en) * | 2015-09-21 | 2015-12-23 | 中国计量学院 | Neodymium-doped bismuth ferrite nanometer photocatalyst and preparation method thereof |
| CN107649141A (en) * | 2017-09-28 | 2018-02-02 | 上海应用技术大学 | Neodymium, nickel are co-doped with the preparation method of bismuth ferrite photocatalyst and its composite catalyst |
| CN108525671A (en) * | 2018-03-29 | 2018-09-14 | 江苏康润净化科技有限公司 | A kind of preparation method of visible light-responded ferrum series photocatalyst |
| CN112892550A (en) * | 2021-01-26 | 2021-06-04 | 暨南大学 | Lanthanum-manganese double-doped bismuth ferrite nano material and preparation method and application thereof |
-
2021
- 2021-11-18 CN CN202111367252.4A patent/CN113941337B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170157A (en) * | 2015-09-21 | 2015-12-23 | 中国计量学院 | Neodymium-doped bismuth ferrite nanometer photocatalyst and preparation method thereof |
| CN107649141A (en) * | 2017-09-28 | 2018-02-02 | 上海应用技术大学 | Neodymium, nickel are co-doped with the preparation method of bismuth ferrite photocatalyst and its composite catalyst |
| CN108525671A (en) * | 2018-03-29 | 2018-09-14 | 江苏康润净化科技有限公司 | A kind of preparation method of visible light-responded ferrum series photocatalyst |
| CN112892550A (en) * | 2021-01-26 | 2021-06-04 | 暨南大学 | Lanthanum-manganese double-doped bismuth ferrite nano material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YAJIE HAN ET AL.: "Time-stable giant energy density and high efficiency in lead free (Ce,Mn)-modified (Na0.8K0.2)0.5Bi0.5TiO3 ceramic film capacitor", 《CERAMICS INTERNATIONAL》 * |
| 郭仁青: "稀土掺杂BiFeO3纳米颗粒的制备及可见光催化性质研究", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115007164A (en) * | 2022-06-27 | 2022-09-06 | 中山大学 | Preparation of rod-shaped bismuth ferrite piezoelectric catalyst and application of rod-shaped bismuth ferrite piezoelectric catalyst in preparation of hydrogen peroxide and hydrogen by catalytic cracking of water |
| CN116371415A (en) * | 2023-04-14 | 2023-07-04 | 哈尔滨工程大学 | Preparation method of cerium doped material for improving catalytic performance of bismuth ferrite |
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