WO2014119814A1 - Visible light sensitive compound, photocatalyst comprising same, and method for manufacturing photocatalyst - Google Patents
Visible light sensitive compound, photocatalyst comprising same, and method for manufacturing photocatalyst Download PDFInfo
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- WO2014119814A1 WO2014119814A1 PCT/KR2013/001172 KR2013001172W WO2014119814A1 WO 2014119814 A1 WO2014119814 A1 WO 2014119814A1 KR 2013001172 W KR2013001172 W KR 2013001172W WO 2014119814 A1 WO2014119814 A1 WO 2014119814A1
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 42
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 19
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910016497 Er(NO3)3.5H2O Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000032900 absorption of visible light Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 229910002915 BiVO4 Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 29
- 230000000694 effects Effects 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- -1 erbium ions Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B01J35/30—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Definitions
- the present invention relates to a visible light sensitive photocatalyst and a method of manufacturing the same, and more particularly, to a visible light sensitive photocatalyst composed of bismuth vanadate (BiVO 4 ) doped with erbium (Er 3+ ) and a method of manufacturing the same.
- a visible light sensitive photocatalyst composed of bismuth vanadate (BiVO 4 ) doped with erbium (Er 3+ ) and a method of manufacturing the same.
- the photocatalyst excites electrons from the valence band to the conduction band when it receives light with energy above the bandgap energy to form electrons in the conduction band and holes in the valence band, and the formed electrons and holes It diffuses to the surface of the photocatalyst and participates in oxidation and reduction reactions.
- Photocatalysis can be used to produce hydrogen, the next-generation alternative energy source, by directly decomposing water using solar energy and decomposing volatile organic compounds (VOCs), various odors, wastewater, hard-degradable pollutants and environmental hormones. It can be used for sterilization of bacteria, bacteria, etc. Therefore, photocatalyst technology using only solar energy at room temperature has attracted attention as a powerful means to solve environmental problems by applying to hydrogen production and environmental purification.
- VOCs volatile organic compounds
- Titanium dioxide which is widely used as a photocatalyst, has excellent properties in decomposing organic matter and water.
- titanium dioxide (TiO 2 ) causes a photocatalytic reaction only in the ultraviolet region containing about 4% of sunlight.
- An object of the present invention is to provide a visible light-sensitive photocatalyst and a method of manufacturing the same, which is doped with erbium (Er 3+ ) to BiVO 4 having high visible light absorption.
- the present invention provides a visible light-sensitive photocatalyst comprising a compound represented by Er 3+ : BiVO 4 , bismuth vanadate (BiVO 4 ) doped with erbium (Er 3+ ), and a method of manufacturing the same.
- the visible light-sensitive photocatalyst is characterized in that it can be expressed as Er 3+ : BiVO 4
- the erbium (Er 3+ ) is characterized in that it is doped at a concentration of 4mol% to 5mol%.
- the visible light-sensitive photocatalyst is characterized by having a rod-shaped crystal structure.
- the photocatalyst according to the present invention has a bandgap energy capable of absorbing visible light, the absorption efficiency of visible light is high, and the effective mass of the charge is small, so that the charge transfer efficiency is high.
- it since it has the energy level of the valence and conduction bands of the potential suitable for decomposing water, it can have a high overvoltage with respect to the oxidation of water, so that the photocatalyst can be used as a water decomposition photocatalyst having high efficiency.
- FIGS. 2A and 2B are graphs of an optical absorption spectrum of a visible light sensitive photocatalyst according to the present invention
- Figure 3a is a photograph taken by SEM of the visible light-sensitive photocatalyst of Comparative Example 1 of the present invention
- 3b is a SEM photograph of the visible light-sensitive photocatalyst of Example 1 of the present invention.
- Figure 4 is a graph of the evaluation of methylene blue decomposition activity of the visible light-sensitive photocatalyst according to the present invention.
- the present invention is a compound represented by Er 3+ : BiVO 4 ;
- the present invention relates to a photocatalyst including the same and a method for preparing the same, and more particularly, to a compound represented by Er 3+ : BiVO 4 ;
- a visible light-sensitive photocatalyst comprising bismuth vanadate (BiVO 4 ) doped with erbium (Er 3+ ) and a method of manufacturing the same.
- the erbium (Er 3+ ) is doped with the bismuth vanadate (BiVO 4 ) to improve crystallinity and may be represented as Er 3+ : BiVO 4 .
- the erbium ions (Er 3+ ) form a trap level in the energy band, thereby improving the afterglow time of bismuth vanadate (BiVO 4 ).
- the doping concentration of the erbium (Er 3+ ) is 2.00 mol% or more and 5.00 mol% or less, and more preferably 4.00 mol% or more and 5.00 mol% or less.
- the doping concentration of erbium is less than 2.00 mol%, it does not give a special change to the undoped bismuth vanadate (BiVO 4 ), and if it is doped at too much concentration, it is effective in the concentration quenching effect. Resulting luminance deterioration.
- the visible light-sensitive photocatalyst is manufactured by using a microwave hydrothermal method, and has an advantage of being easily formed in a one-step process without going through a complicated process.
- ion-exchanged water 60 ml of ion-exchanged water is prepared. Thereafter, 0.005 mol% of NH 4 VO 3 was added to the ion-exchanged water and mixed to prepare a first solution.
- ion-exchanged water 20 ml of ion-exchanged water was prepared, a second solution was prepared by adding 0.005 mol% of Bi (NO 3 ) 3 .5H 2 O and 20 ml of Acetic acid, and then mixed with the first solution to prepare a mixed solution. . Then, after adding and mixing the added amount of Er (NO 3) 3 ⁇ 5H 2 O 4.00 mol% in the mixture, using the ammonia solution to form a pH9. Thereafter, 30 minutes were baked at 140 ° C. using the microwave hydrothermal method. Then, washed with ion-exchanged water to remove impurities, dried at 70 °C, and calcined at 300 °C for 2 hours to complete the visible light-sensitive photocatalyst.
- Example 2 the concentration of the doped erbium of Example 1 was set to 5.00 mol%, and other portions were the same as in Example 1, thereby completing the solid visible light-sensitized photocatalyst according to Example 2.
- Comparative Example 1 the concentration of the doped erbium of Example 1 was set to 0.00 mol%, and the other part was the same as Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 1.
- Example 2 the concentration of the doped erbium of Example 1 was 0.25 mol%, and the other part was the same as Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 2.
- Comparative Example 3 the concentration of the doped erbium of Example 1 was 0.50 mol%, and other portions were the same as in Example 1, thereby completing the solid visible light-sensitized photocatalyst according to Comparative Example 3.
- Comparative Example 4 only the concentration of the doped erbium of Example 1 was 0.75 mol%, and the other part was the same as in Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 4.
- Comparative Example 5 only the concentration of the doped erbium of Example 1 was 1.00 mol%, and the other part was the same as in Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 5.
- Comparative Example 6 the concentration of the doped erbium of Example 1 was set to 2.00 mol%, and the other part was the same as Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 6.
- Comparative Example 7 the concentration of the doped erbium of Example 1 was set to 3.00 mol%, and other portions were the same as in Example 1, thereby completing a solid visible light-sensitized photocatalyst according to Comparative Example 7.
- FIG. 1 shows an X-ray diffraction spectrum of a visible light sensitive photocatalyst according to the present invention.
- FIG. 1 when the X-ray spectra of Comparative Examples 1 to 7 and Examples 1 to 2 according to the present invention are examined, when the doping amount of erbium is increased to 2 mol% or more, tetragonal It can be seen that a peak appears.
- Examples 1 to 2 where the doping concentration of erbium is 4 mol% or more, a very strong tetragonal peak can be observed, which is a 4 mol% doping concentration of erbium.
- Figure 2a shows the amount of doped erbium (Er 3+ ) 0.00mol%, 0.25 mol%, 0.50 mol%, 0.75 mol %, 1.00 mol%
- the optical absorption spectrum of Comparative Examples 1 to 5 was measured
- FIG. 2B shows the amounts of doped erbium (Er 3+ ) 2.00 mol%, 3.00 mol%, 4.00 mol%
- the spectrum of sunlight includes ultraviolet light in the range of about 200-400 nm, visible light in the range of about 400-750 nm and infrared light of at least about 750 nm.
- Ultraviolet light is a very small part of sunlight, and visible light and infrared light make up most of sunlight.
- a material having a wide bandgap energy of about 3.2 eV absorbs only ultraviolet rays
- a material having a bandgap energy of less than that should be used and in the case of bismuth vanadate (BiVO 4 ) doped with erbium according to the present invention, it is 2.9.
- the erbium ions are stabilized because they have a bandgap of eV, and in the case of Examples 1 and 2, it is well understood that strongly absorbs light having a wavelength of 400 to 500.
- FIG. 3A is a SEM photograph of the visible light sensitive photocatalyst of Comparative Example 1 of the present invention
- FIG. 3B is a photograph photographing the visible light sensitive photocatalyst of Example 1 of the present invention (JSM-6400, JEOL).
- the bismuth vanadate (BiVO 4 ) that is not doped with erbium (Er 3+ ) has a micro sized needle shape, and is more uniform in the case of FIG. 3B that is doped with erbium (Er 3+ ). It is in the form of a needle, and it can be seen that when erbium (Er 3+ ) is doped with bismuth vanadate (BiVO 4 ), the shape becomes more uniform without affecting the shape change.
- Figure 4 is a graph of the evaluation of methylene blue decomposition activity of the visible light-sensitive photocatalyst according to the present invention.
- 0.05 g of the photocatalyst according to the present invention in the form of a powder in a reaction vessel was mixed with 50 ml of methylene blue aqueous solution (5 ppm) and irradiated with a solar simulator (AM 1.5G).
- Decomposition efficiency is measured in the UV-Vis device by detecting the methylene blue aqueous solution according to each time.
- the photocatalyst formed by the microwave hydrothermal method according to the present invention has much higher activity than the conventional photocatalyst by coprecipitation.
- the concentration of erbium was 4 mol% and 5 mol%
- the visible light sensitive photocatalyst described herein is only one embodiment, and the present invention is not limited to the embodiment. In addition, it will be easy for those skilled in the art to apply and modify the technology within the predictable range.
Abstract
The present invention relates to a visible light sensitive photocatalyst and a method for manufacturing the same, and is characterized in that the visible light sensitive photocatalyst contains an erbium (Er3+)-doped bismuth vanadate (BiVO4) compound, the compound being prepared by a microwave hydrothermal synthesis method. The photocatalyst according to the present invention has band gap energy allowing absorption of visible light and thus exhibits high absorption efficiency of visible light, and has a small effective mass of charges and thus exhibits high charge transfer efficiency. In addition, the photocatalyst has valence and conduction band energy levels corresponding to potentials suitable for the decomposition of water and thus can have a high overvoltage to the oxidation of water. Therefore, the photocatalyst according to the present invention can be used as a highly efficient water decomposing photocatalyst with high efficiency.
Description
본 발명은 가시광 감응 광촉매 및 그의 제조방법에 관한 것으로서, 더욱 상세하게는 어븀(Er3+)이 도핑된 비스무스 바나데이트(BiVO4)로 이루어진 가시광 감응 광촉매 및 그의 제조 방법에 관한 것이다.The present invention relates to a visible light sensitive photocatalyst and a method of manufacturing the same, and more particularly, to a visible light sensitive photocatalyst composed of bismuth vanadate (BiVO 4 ) doped with erbium (Er 3+ ) and a method of manufacturing the same.
광촉매(photocatalyst)는 밴드갭 에너지 이상의 에너지를 갖는 빛을 받으면 가전자대(valence band)에서 전도대 (conduction band)로 전자를 여기시켜서 전도대에는 전자를 형성하고 가전자대에는 정공을 형성하며, 형성된 전자와 정공이 광촉매의 표면으로 확산하여 산화, 환원 반응에 참여한다.The photocatalyst excites electrons from the valence band to the conduction band when it receives light with energy above the bandgap energy to form electrons in the conduction band and holes in the valence band, and the formed electrons and holes It diffuses to the surface of the photocatalyst and participates in oxidation and reduction reactions.
광촉매 반응(photocatalysis)은 태양 에너지를 이용하여 물을 직접 광분해하여 차세대의 대체 에너지원인 수소를 생산하는데 사용될 수 있으며, 휘발성 유기화합물(VOCs), 각종 악취, 폐수, 난분해성 오염물질 및 환경 호르몬의 분해, 세균, 박테리아의 살균 등에 사용될 수 있다. 따라서 상온에서 태양 에너지만을 사용하는 광촉매 기술은 수소 제조 및 환경 정화에 응용되어 환경 문제를 해결할 수 있는 유력한 수단으로 주목을 받고 있다.Photocatalysis can be used to produce hydrogen, the next-generation alternative energy source, by directly decomposing water using solar energy and decomposing volatile organic compounds (VOCs), various odors, wastewater, hard-degradable pollutants and environmental hormones. It can be used for sterilization of bacteria, bacteria, etc. Therefore, photocatalyst technology using only solar energy at room temperature has attracted attention as a powerful means to solve environmental problems by applying to hydrogen production and environmental purification.
현재 광촉매로서로 폭넓게 사용되고 있는 이산화티탄(TiO2)은 유기물 및 물을 분해하는데 우수한 특성을 나타내고 있다. 그러나 이산화티탄(TiO2)은 태양광의 4% 정도를 포함하는 자외선 영역에서만 광촉매 반응을 일으킨다.Titanium dioxide (TiO 2 ), which is widely used as a photocatalyst, has excellent properties in decomposing organic matter and water. However, titanium dioxide (TiO 2 ) causes a photocatalytic reaction only in the ultraviolet region containing about 4% of sunlight.
따라서 광촉매 기술을 효과적으로 활용하기 위하여는 태양광의 약 43%를 차지하는 가시광을 효과적으로 이용할수 있는 높은 가시광 활성을 가진 광촉매 재료의 개발이 필요하다.Therefore, in order to effectively utilize the photocatalyst technology, it is necessary to develop a photocatalyst material having high visible light activity that can effectively use visible light, which accounts for about 43% of sunlight.
본 발명은 기존의 가시광 흡수율이 높은 BiVO4에 어븀(Er3+)을 도핑하여, 기능이 향상된 가시광 감응 광촉매 및 그의 제조방법을 제공하는데 목적이 있다.An object of the present invention is to provide a visible light-sensitive photocatalyst and a method of manufacturing the same, which is doped with erbium (Er 3+ ) to BiVO 4 having high visible light absorption.
본 발명은 Er3+:BiVO4 로 표시되는 화합물, 어븀(Er3+)이 도핑된 비스무스 바나데이트(BiVO4)를 포함하는 가시광 감응 광촉매 및 그의 제조방법을 제공한다.The present invention provides a visible light-sensitive photocatalyst comprising a compound represented by Er 3+ : BiVO 4 , bismuth vanadate (BiVO 4 ) doped with erbium (Er 3+ ), and a method of manufacturing the same.
더 자세하게는, 상기 가시광 감응 광촉매는 Er3+:BiVO4로 표시할 수 있는 것을 특징으로 하며, 상기 어븀(Er3+)은 4mol% 내지 5mol%의 농도로 도핑된 것임을 특징으로 한다.More specifically, the visible light-sensitive photocatalyst is characterized in that it can be expressed as Er 3+ : BiVO 4 , the erbium (Er 3+ ) is characterized in that it is doped at a concentration of 4mol% to 5mol%.
그리고 상기 가시광 감응 광촉매는 막대형 결정구조를 갖는 것을 특징으로 한다.The visible light-sensitive photocatalyst is characterized by having a rod-shaped crystal structure.
본 발명에 따른 광촉매는 가시광을 흡수할 수 있는 밴드갭 에너지를 갖기 때문에 가시광의 흡수 효율이 높고, 전하의 유효질량이 작아서 전하의 전송 효율이 높다. 또한, 물을 분해하기에 적합한 전위의 가전자대와 전도대의 에너지 레벨을 가지므로 물의 산화에 대하여 높은 과전압을 가질 수 있어서 상기 광촉매는 높은 효율을 갖는 물 분해 광촉매로 사용될 수 있다.Since the photocatalyst according to the present invention has a bandgap energy capable of absorbing visible light, the absorption efficiency of visible light is high, and the effective mass of the charge is small, so that the charge transfer efficiency is high. In addition, since it has the energy level of the valence and conduction bands of the potential suitable for decomposing water, it can have a high overvoltage with respect to the oxidation of water, so that the photocatalyst can be used as a water decomposition photocatalyst having high efficiency.
도 1은 본 발명에 따른 본 발명에 따른 X선 회절 스펙트럼에 관한 그래프이며,1 is a graph of the X-ray diffraction spectrum according to the present invention according to the present invention,
도 2a 및 2b는 본 발명에 따른 가시광 감응 광촉매의 광학 흡수 스펙트럼에 관한 그래프이며,2A and 2B are graphs of an optical absorption spectrum of a visible light sensitive photocatalyst according to the present invention,
도 3a는 본 발명의 비교예 1의 가시광 감응 광촉매를 SEM으로 촬영한 사진이고, Figure 3a is a photograph taken by SEM of the visible light-sensitive photocatalyst of Comparative Example 1 of the present invention,
도 3b는 본 발명의 실시예 1의 가시광 감응 광촉매를 SEM으로 촬영한 사진이고,3b is a SEM photograph of the visible light-sensitive photocatalyst of Example 1 of the present invention;
도 4는 본 발명에 따른 가시광 감응 광촉매의 메틸렌 블루 분해활성 평가에 관한 그래프이다.Figure 4 is a graph of the evaluation of methylene blue decomposition activity of the visible light-sensitive photocatalyst according to the present invention.
이하, 실시예를 참조하여 본 발명을 서술한다. 상세한 설명, 도면들 및 청구항들에서 상술하는 예시적인 실시예들은 한정을 위한 것이 아니며, 다른 실시예들이 이용될 수 있으며, 여기서 개시되는 요부(subject matter)의 사상이나 범주를 벗어나지 않는 한 다른 변경들도 가능하다. 본 개시의 구성요소들, 즉 여기서 일반적으로 기술되고 및 도면에 기재되는 구성요소들은 다양하게 다른 구성으로 배열되고, 치환되고, 결합되고, 도안될 수 있으며, 이것들의 모두는 명백하게 예상 되며, 본 개시의 일부를 형성하고 있음을 용이하게 이해할 수 있을 것이다. Hereinafter, this invention is described with reference to an Example. The illustrative embodiments described above in the detailed description, drawings, and claims are not meant to be limiting, other embodiments may be utilized, and other changes may be made without departing from the spirit or scope of the subject matter disclosed herein. It is also possible. The components of the present disclosure, that is, those described generally herein and described in the figures, may be arranged, substituted, combined, and designed in a variety of different configurations, all of which are expressly expected and It will be readily understood that they form part of.
이하, 본 발명의 일 측면에 따라 본 발명을 설명한다.Hereinafter, the present invention will be described according to one aspect of the present invention.
본 발명은 Er3+:BiVO4로 표시되는 화합물; 이를 포함하는 광촉매 및 그의 제조방법에 관한 것으로, 더 자세하게는 Er3+:BiVO4로 표시되는 화합물; 어븀(Er3+)이 도핑된 비스무스 바나데이트(BiVO4)를 포함하는 가시광 감응 광촉매 및 그의 제조방법에 관한 것이다.The present invention is a compound represented by Er 3+ : BiVO 4 ; The present invention relates to a photocatalyst including the same and a method for preparing the same, and more particularly, to a compound represented by Er 3+ : BiVO 4 ; A visible light-sensitive photocatalyst comprising bismuth vanadate (BiVO 4 ) doped with erbium (Er 3+ ) and a method of manufacturing the same.
상기 어븀(Er3+)은 상기 비스무스 바나데이트(BiVO4)에 도핑된 형태로 위치하여 결정성을 우수하게 하고, Er3+:BiVO4 로 표시될 수 있다. 상기 어븀 이온(Er3+)은 에너지 밴드에서 트랩(trap) 준위를 형성하여 비스무스 바나데이트(BiVO4)의 잔광시간의 향상을 가져온다.The erbium (Er 3+ ) is doped with the bismuth vanadate (BiVO 4 ) to improve crystallinity and may be represented as Er 3+ : BiVO 4 . The erbium ions (Er 3+ ) form a trap level in the energy band, thereby improving the afterglow time of bismuth vanadate (BiVO 4 ).
이때, 상기 어븀(Er3+)의 도핑농도는 2.00mol%이상 5.00mol%이하로 하고, 더 바람직하게는 4.00mol%이상 5.00mol%이하로 한다. 그 이유는 어븀의 도핑농도를 2.00mol%미만으로 한 경우, 도핑이 되지 않은 비스무스 바나데이트(BiVO4)에 특별한 변화를 주지 못하고, 너무 많은 농도로 도핑하면, 농도켄칭효과(concentration quenching effect)에 따른 휘도 저하가 나타난다.In this case, the doping concentration of the erbium (Er 3+ ) is 2.00 mol% or more and 5.00 mol% or less, and more preferably 4.00 mol% or more and 5.00 mol% or less. The reason is that when the doping concentration of erbium is less than 2.00 mol%, it does not give a special change to the undoped bismuth vanadate (BiVO 4 ), and if it is doped at too much concentration, it is effective in the concentration quenching effect. Resulting luminance deterioration.
상기 가시광 감응 광촉매는 마이크로웨이브 수열합성 방법(microwave hydrothermal method)를 이용하여 제조하는 것으로써, 복잡한 여러공정을 거치지 않고, 1-step의 과정으로 용이하게 형성할 수 있는 장점이 있다.The visible light-sensitive photocatalyst is manufactured by using a microwave hydrothermal method, and has an advantage of being easily formed in a one-step process without going through a complicated process.
이하, 본 발명에 따른 가시광 감응 광촉매의 제조방법의 일 실시예이다.Hereinafter, one embodiment of a method of manufacturing a visible light-sensitive photocatalyst according to the present invention.
<실시예 1><Example 1>
우선, 이온교환수 60 ml를 준비한다. 그리고 나서, 상기 이온교환수에 NH4VO3 를 0.005 mol%를 첨가하여 혼합하여 제 1용액을 준비하였다. First, 60 ml of ion-exchanged water is prepared. Thereafter, 0.005 mol% of NH 4 VO 3 was added to the ion-exchanged water and mixed to prepare a first solution.
그 후에 이온교환수 20 ml를 준비하고, Bi(NO3)3·5H2O 0.005 mol%와 Acetic acid 20 ml를 첨가하여 제 2 용액을 준비한 후, 상기 제 1 용액과 혼합하여 혼합액을 준비하였다. 그리고 나서, 상기 혼합액에 Er(NO3)3·5H2O의 첨가량을 4.00 mol % 첨가하여 혼합한 후, ammonia solution을 이용하여 pH9를 형성하였다. 그 후에, 마이크로웨이브 수열합성 방법(Microwave hydrothermal method)을 이용하여 140 ℃에서 30분을 소성하였다. 그리고 나서, 불순물 제거를 위하여 이온교환수를 이용하여 세척한 후, 70 ℃에서 건조하고, 300 ℃에서 2시간 동안 하소하는 단계를 거쳐 가시광 감응 광촉매를 완성하였다.Thereafter, 20 ml of ion-exchanged water was prepared, a second solution was prepared by adding 0.005 mol% of Bi (NO 3 ) 3 .5H 2 O and 20 ml of Acetic acid, and then mixed with the first solution to prepare a mixed solution. . Then, after adding and mixing the added amount of Er (NO 3) 3 · 5H 2 O 4.00 mol% in the mixture, using the ammonia solution to form a pH9. Thereafter, 30 minutes were baked at 140 ° C. using the microwave hydrothermal method. Then, washed with ion-exchanged water to remove impurities, dried at 70 ℃, and calcined at 300 ℃ for 2 hours to complete the visible light-sensitive photocatalyst.
<실시예 2><Example 2>
실시예 2는 상기 실시예 1의 도핑한 어븀의 농도를 5.00 mol %로 하였을 뿐, 다른 부분은 상기 실시예 1과 동일하게 하여 실시예 2에 따른 고체의 가시광 감응 광촉매를 완성하였다.In Example 2, the concentration of the doped erbium of Example 1 was set to 5.00 mol%, and other portions were the same as in Example 1, thereby completing the solid visible light-sensitized photocatalyst according to Example 2.
<비교예1>Comparative Example 1
비교예 1은 상기 실시예 1의 도핑한 어븀의 농도를 0.00 mol %로 하였을 뿐, 다른 부분은 상기 실시예 1과 동일하게 하여 비교예 1에 따른 고체의 가시광 감응 광촉매를 완성하였다.In Comparative Example 1, the concentration of the doped erbium of Example 1 was set to 0.00 mol%, and the other part was the same as Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 1.
<비교예2>Comparative Example 2
비교예 2는 상기 실시예 1의 도핑한 어븀의 농도를 0.25 mol %로 하였을 뿐, 다른 부분은 상기 실시예 1과 동일하게 하여 비교예 2에 따른 고체의 가시광 감응 광촉매를 완성하였다.In Comparative Example 2, the concentration of the doped erbium of Example 1 was 0.25 mol%, and the other part was the same as Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 2.
<비교예3>Comparative Example 3
비교예 3은 상기 실시예 1의 도핑한 어븀의 농도를 0.50 mol %로 하였을 뿐, 다른 부분은 상기 실시예 1과 동일하게 하여 비교예 3에 따른 고체의 가시광 감응 광촉매를 완성하였다.In Comparative Example 3, the concentration of the doped erbium of Example 1 was 0.50 mol%, and other portions were the same as in Example 1, thereby completing the solid visible light-sensitized photocatalyst according to Comparative Example 3.
<비교예4>Comparative Example 4
비교예 4은 상기 실시예 1의 도핑한 어븀의 농도를 0.75 mol %로 하였을 뿐, 다른 부분은 상기 실시예 1과 동일하게 하여 비교예 4에 따른 고체의 가시광 감응 광촉매를 완성하였다.In Comparative Example 4, only the concentration of the doped erbium of Example 1 was 0.75 mol%, and the other part was the same as in Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 4.
<비교예5>Comparative Example 5
비교예 5는 상기 실시예 1의 도핑한 어븀의 농도를 1.00 mol %로 하였을 뿐, 다른 부분은 상기 실시예 1과 동일하게 하여 비교예 5에 따른 고체의 가시광 감응 광촉매를 완성하였다.In Comparative Example 5, only the concentration of the doped erbium of Example 1 was 1.00 mol%, and the other part was the same as in Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 5.
<비교예6>Comparative Example 6
비교예 6은 상기 실시예 1의 도핑한 어븀의 농도를 2.00 mol %로 하였을 뿐, 다른 부분은 상기 실시예 1과 동일하게 하여 비교예 6에 따른 고체의 가시광 감응 광촉매를 완성하였다.In Comparative Example 6, the concentration of the doped erbium of Example 1 was set to 2.00 mol%, and the other part was the same as Example 1 to complete the visible light-sensitive photocatalyst of the solid according to Comparative Example 6.
<비교예7>Comparative Example 7
비교예 7은 상기 실시예 1의 도핑한 어븀의 농도를 3.00 mol %로 하였을 뿐, 다른 부분은 상기 실시예 1과 동일하게 하여 비교예 7에 따른 고체의 가시광 감응 광촉매를 완성하였다.In Comparative Example 7, the concentration of the doped erbium of Example 1 was set to 3.00 mol%, and other portions were the same as in Example 1, thereby completing a solid visible light-sensitized photocatalyst according to Comparative Example 7.
이하, 도 1은 본 발명에 따른 가시광 감응 광촉매의 X-선 회절 스펙트럼을 나타낸다. 도 1을 참조하면, 본 발명에 따른 비교예 1 내지 비교예 7 및 실시예 1 내지 실시예 2의 X-선 스펙트럼을 살펴본 결과 어븀의 도핑량이 증가하여 2 mol% 이상인 경우 정방정계(tetragonal)의 피크(peak)가 나타남을 알 수 있다. 특히, 어븀의 도핑농도를 4 mol% 이상으로 한 실시예 1 내지 실시예 2의 경우, 매우 강한 정방정계(tetragonal)의 피크(peak)를 관찰할 수 있는데, 이것은 어븀의 도핑농도를 4 mol% 이상으로 한 경우에 비스무스 바나데이트(BiVO4)에 어븀이 잘 도핑되었다고 판단할 수 있는 것이다.1 shows an X-ray diffraction spectrum of a visible light sensitive photocatalyst according to the present invention. Referring to FIG. 1, when the X-ray spectra of Comparative Examples 1 to 7 and Examples 1 to 2 according to the present invention are examined, when the doping amount of erbium is increased to 2 mol% or more, tetragonal It can be seen that a peak appears. In particular, in Examples 1 to 2 where the doping concentration of erbium is 4 mol% or more, a very strong tetragonal peak can be observed, which is a 4 mol% doping concentration of erbium. In this case, it can be judged that bismuth vanadate (BiVO 4 ) is well doped with erbium.
그리고 도 2a 및 2b는 본 발명에 따른 가시광 감응 광촉매의 광학 흡수 스펙트럼에 관한 것으로써, 도 2a는 도핑된 어븀(Er3+)의 양을 0.00mol%, 0.25 mol%, 0.50 mol%, 0.75 mol%, 1.00mol%으로 한, 비교예 1 내지 비교예 5의 광학 흡수 스펙트럼을 측정한 것이고, 도 2b는 도핑된 어븀(Er3+)의 양을 2.00mol%, 3.00 mol%, 4.00 mol%, 5.00mol%으로 다르게 한 비교예 6 및 비교예 7, 실시예 1 내지 실시예 2의 광학 흡수 스펙트럼을 측정한 것이다.And 2a and 2b relates to the optical absorption spectrum of the visible light-sensitive photocatalyst according to the present invention, Figure 2a shows the amount of doped erbium (Er 3+ ) 0.00mol%, 0.25 mol%, 0.50 mol%, 0.75 mol %, 1.00 mol%, the optical absorption spectrum of Comparative Examples 1 to 5 was measured, and FIG. 2B shows the amounts of doped erbium (Er 3+ ) 2.00 mol%, 3.00 mol%, 4.00 mol%, The optical absorption spectra of Comparative Example 6 and Comparative Example 7, Examples 1 to 2, which were changed to 5.00 mol%, were measured.
도 2a를 참조하면, 어븀(Er3+)을 0.25 mol%, 0.50 mol%, 0.75 mol% 및 1.00mol%로 하여 비스무스 바나데이트(BiVO4)에 도핑한 경우, 어븀(Er3+)을 도핑하지 않은 비스무스 바나데이트(BiVO4)와의 광학 흡수 스펙트럼이 차이를 보이지 않는다는 것을 확인하여, 상기 농도의 어븀의 도핑이 비스무스 바나데이트에 영향을 주지 않는다는 것을 알 수 있다. Referring to FIG. 2A, when the bismuth vanadate (BiVO 4 ) is doped with erbium (Er 3+ ) at 0.25 mol%, 0.50 mol%, 0.75 mol%, and 1.00 mol%, erbium (Er 3+ ) is doped. It can be seen that the optical absorption spectrum with bismuth vanadate (BiVO 4 ), which does not show no difference, shows that doping of the erbium at this concentration does not affect bismuth vanadate.
반면, 도 2b를 참조하면, 어븀(Er3+)을2.00 mol%, 3.00 mol%, 4.00 mol% 및 5.00 mol%로 하여 비스무스 바나데이트(BiVO4)에 도핑한 경우인 비교예6 및 비교예7, 실시예 1 및 실시예 2의 경우를 살펴보면, 실시예 1 및 실시예 2의 경우, 522nm와 653nm의 파장에서 날카로운 두개의 피크(peak)를 발견할 수 있었다. 이것은 522nm에서는 I15/2와 H11/2 상태 사이의 전이 에너지와 잘 일치하여 두 이온 간의 효율적인 공명 에너지 전달이 일어남을 알 수 있는 것이다. 따라서, 도핑된 어븀이온(Er3+)이 비스무스 바나데이트에 에너지를 전달을 해주는 것이다.On the other hand, referring to Figure 2b, Comparative Example 6 and Comparative Example in the case of doping bismuth vanadate (BiVO 4 ) with Erbium (Er 3+ ) 2.00 mol%, 3.00 mol%, 4.00 mol% and 5.00 mol% Referring to the case of 7, Example 1 and Example 2, in the case of Examples 1 and 2, two sharp peaks were found at the wavelength of 522nm and 653nm. This is in good agreement with the transition energy between the I 15/2 and H 11/2 states at 522 nm, indicating that efficient resonance energy transfer between the two ions occurs. Therefore, doped erbium ions (Er 3+ ) is to transfer energy to bismuth vanadate.
특히, 어븀(Er3+)의 농도를 4.00 mol% 및 5.00 mol%, 로 비스무스 바나데이트(BiVO4)에 도핑한 경우, 400nm~500nm사이에서 정방정계(tetragonal)과 단사정계(monoclinic)의 두개의 혼합된 상이 나타났으며, 이것은 원래는 단사정계이지만, 어븀이 도핑된 농도가 4 mol% 이상이 되면, 정방정계가 나타나며, 두가지 복합구조의 형태에서 최적의 광촉매 효과가 나타난다는 것을 의미한다. In particular, when doped with erbium (Er 3+ ) concentrations of 4.00 mol% and 5.00 mol%, low bismuth vanadate (BiVO 4 ), two tetragonal and monoclinic systems between 400 nm and 500 nm The mixed phase of was shown, which was originally monoclinic but when the concentration of the erbium doped concentration was more than 4 mol%, a tetragonal system appeared, which means that the optimum photocatalytic effect was obtained in the form of two complex structures.
태양광의 스펙트럼은 약 200-400 ㎚ 범위의 자외선과 약 400-750 ㎚ 범위의 가시광선과 약 750 ㎚ 이상의 적외선을 포함한다. 자외선은 태양광의 극히 일부이며, 가시광선과 적외선이 태양광의 대부분을 구성하고 있다. 이때, 약 3.2 eV 정도의 넓은 밴드갭 에너지를 갖는 물질은 자외선만을 흡수하므로 그 이하의 밴드갭 에너지를 갖는 물질을 사용해야 하며, 본 발명에 따른 어븀이 도핑된 비스무스 바나데이트(BiVO4)의 경우 2.9eV의 밴드갭을 가지므로 어븀이온이 안정화되어 있다는 것을 알 수 있으며, 실시예 1 및 실시예 2의 경우 400 내지 500의 파장의 빛을 강하게 흡수하는 것을 잘 알 수 있다.The spectrum of sunlight includes ultraviolet light in the range of about 200-400 nm, visible light in the range of about 400-750 nm and infrared light of at least about 750 nm. Ultraviolet light is a very small part of sunlight, and visible light and infrared light make up most of sunlight. At this time, since a material having a wide bandgap energy of about 3.2 eV absorbs only ultraviolet rays, a material having a bandgap energy of less than that should be used, and in the case of bismuth vanadate (BiVO 4 ) doped with erbium according to the present invention, it is 2.9. It can be seen that the erbium ions are stabilized because they have a bandgap of eV, and in the case of Examples 1 and 2, it is well understood that strongly absorbs light having a wavelength of 400 to 500.
도 3a는 본 발명의 비교예 1의 가시광 감응 광촉매를 SEM으로 촬영한 것이고, 도 3b는 본 발명의 실시예 1의 가시광 감응 광촉매를 SEM으로 촬영한 사진이다(JSM-6400, JEOL). 3A is a SEM photograph of the visible light sensitive photocatalyst of Comparative Example 1 of the present invention, and FIG. 3B is a photograph photographing the visible light sensitive photocatalyst of Example 1 of the present invention (JSM-6400, JEOL).
상기 도 3a를 살펴보면, 어븀(Er3+)이 도핑되지 않은 비스무스 바나데이트(BiVO4)인 경우에는 마이크로 크기의 바늘형태이며, 어븀(Er3+)이 도핑된 도 3b의 경우에는 보다 균일한 바늘형태를 하고 있어, 어븀(Er3+)이 비스무스 바나데이트(BiVO4)에 도핑되면 형태변화에는 영향을 주지 않고 형태가 더 균일하게 된다는 것을 알 수 있다.Referring to FIG. 3A, the bismuth vanadate (BiVO 4 ) that is not doped with erbium (Er 3+ ) has a micro sized needle shape, and is more uniform in the case of FIG. 3B that is doped with erbium (Er 3+ ). It is in the form of a needle, and it can be seen that when erbium (Er 3+ ) is doped with bismuth vanadate (BiVO 4 ), the shape becomes more uniform without affecting the shape change.
도 4는 본 발명에 따른 가시광 감응 광촉매의 메틸렌 블루 분해활성 평가에 관한 그래프이다. 반응용기에 0.05g의 본 발명에 따른 광촉매를 분말형태로 하여 50 ml의 메틸렌블루 수용액 (5 ppm)에 혼합하고 solar simulator(AM 1.5G)를 조사한다. 각 시간에 따라 메틸렌 블루 수용액을 검출하여 UV-Vis 장치에서 분해 효율을 측정한 그래프이다.Figure 4 is a graph of the evaluation of methylene blue decomposition activity of the visible light-sensitive photocatalyst according to the present invention. 0.05 g of the photocatalyst according to the present invention in the form of a powder in a reaction vessel was mixed with 50 ml of methylene blue aqueous solution (5 ppm) and irradiated with a solar simulator (AM 1.5G). Decomposition efficiency is measured in the UV-Vis device by detecting the methylene blue aqueous solution according to each time.
도 4를 참조하면, 본 발명에 따른 마이크로웨이브 수열합성 방법(microwave hydrothermal method)에 의해 형성한 광촉매의 경우 기존의 공침법(coprecipitation)에 의한 광촉매보다 활성도가 훨씬 우수하다는 것을 알 수 있다. 또한, 어븀의 농도를 4 mol% 및 5 mol%로 한 실시예 1 및 실시예 2의 경우 본 발명의 단사정계(monoclinic)과 정방정계(tetragonal)의 두개의 혼합된 상이 존재하며, 활성이 훨씬 더 뛰어난 것을 알 수 있었다.Referring to FIG. 4, it can be seen that the photocatalyst formed by the microwave hydrothermal method according to the present invention has much higher activity than the conventional photocatalyst by coprecipitation. In addition, in Examples 1 and 2, where the concentration of erbium was 4 mol% and 5 mol%, there were two mixed phases of the monoclinic and tetragonal phases of the present invention, and the activity was much higher. I could see better.
따라서, 상기와 같이 가시광선의 흡수능력이 우수한 비스무스 바나데이트(BiVO4)에 형광의 성질을 갖는 어븀(Er3+)을 도핑하여 종래의 물질보다 더 우수한 가시광 감응의 화합물을 형성함으로써, 그를 이용한 우수한 활성을 갖는 가시광 감응 광촉매를 완성하였다. 또한, 어븀(Er3+)의 농도를 다르게 함으로써, 성능이 우수한 광촉매를 형성할 수 있다.Thus, by doping bismuth vanadate (BiVO 4 ) having excellent absorption of visible light as described above, erbium (Er 3+ ) having a fluorescence property to form a compound having better visible light sensitivity than the conventional material, A visible light sensitive photocatalyst having activity was completed. In addition, by varying the concentration of erbium (Er 3+ ), it is possible to form a photocatalyst having excellent performance.
본 명세서에서 기술된 가시광 감응 광촉매는 일실시예일 뿐 본 발명이 실시예에 한정되는 것이 아니다. 또한, 당업자라면 예측이 가능한 범위안에서 기술의 응용 및 변형이 용이할 것이다. The visible light sensitive photocatalyst described herein is only one embodiment, and the present invention is not limited to the embodiment. In addition, it will be easy for those skilled in the art to apply and modify the technology within the predictable range.
Claims (14)
- 화학식 1로 표시되는 화합물.Compound represented by the formula (1).[화학식 1][Formula 1]Er3+:BiVO4 Er 3+ : BiVO 4
- 제 1항에 있어서,The method of claim 1,상기 화합물은 마이크로웨이브 수열합성 방법으로 형성하는 것을 특징으로 하는 화합물.The compound is formed by the microwave hydrothermal method.
- 제 1항에 있어서,The method of claim 1,상기 화합물은 어븀(Er3+)이 4mol% 내지 5mol%로 비스무스 바나데이트(BiVO4)에 포함하는 것을 특징으로 하는 화합물.The compound is characterized in that the erbium (Er 3+ ) is contained in bismuth vanadate (BiVO 4 ) at 4 mol% to 5 mol%.
- 제 3항에 있어서,The method of claim 3, wherein상기 화합물은 광촉매로 사용할 수 있는 것을 특징으로 하는 화합물.The compound may be used as a photocatalyst.
- 제 1항에 있어서,The method of claim 1,상기 화합물은 2.9eV의 밴드갭을 갖는 것을 특징으로 하는 화합물.The compound having a bandgap of 2.9 eV.
- 상기 제 1항의 화합물을 포함하는 가시광 감응 광촉매.A visible light sensitive photocatalyst comprising the compound of claim 1.
- 제 6항에 있어서,The method of claim 6,상기 광촉매는 Er3+:BiVO4로 표시하는 것을 특징으로 하는 가시광 감응 광촉매.The photocatalyst is a visible light sensitive photocatalyst, characterized in that Er 3+ : BiVO 4 .
- 제 7항에 있어서,The method of claim 7, wherein상기 광촉매는 어븀(Er3+) 이 BiVO4에 도핑된 것인 것을 특징으로 하는 가시광 감응 광촉매.The photocatalyst is a visible light-sensitive photocatalyst, characterized in that the erbium (Er 3+) is doped in BiVO 4 .
- 제 8항에 있어서,The method of claim 8,상기 어븀(Er3+)이 도핑된 농도는 4mol% 내지 5mol%인 것을 특징으로 하는 가시광 감응 광촉매.The erbium (Er 3+ ) doped concentration is visible light sensitive photocatalyst, characterized in that 4mol% to 5mol%.
- 제 6항에 있어서,The method of claim 6,상기 가시광 감응 광촉매는 막대형 결정구조를 갖는 것을 특징으로 하는 가시광 감응 광촉매.The visible light sensitive photocatalyst is a visible light sensitive photocatalyst, characterized in that it has a rod-shaped crystal structure.
- 제 6항에 있어서,The method of claim 6,상기 가시광 감응 광촉매는 2.9 eV의 밴드갭을 갖는 것을 특징으로 하는 가시광 감응 광촉매. The visible light sensitive photocatalyst has a band gap of 2.9 eV.
- NH4VO3 수용액, Bi(NO3)3·5H2O 수용액 및Er(NO3)3·5H2O 수용액을 혼합하여 혼합액을 형성하고,NH 4 VO 3 aqueous solution, Bi (NO 3 ) 3 · 5H 2 O aqueous solution and Er (NO 3 ) 3 · 5H 2 O aqueous solution are mixed to form a mixed solution,상기 혼합액을 마이크로웨이브 수열합성 방법(microwave hydrothermal method)으로 소성하고,The mixed solution is calcined by microwave hydrothermal method,상기 소성된 혼합액을 세척, 건조, 하소하는 단계를 거쳐 고체의 광촉매를 형성하는 것을 특징으로 하는 가시광 감응 광촉매의 제조방법.Method for producing a visible light-sensitive photocatalyst, characterized in that to form a solid photocatalyst through the step of washing, drying, calcining the calcined mixture.
- 제 12항에 있어서,The method of claim 12,상기 마이크로웨이브 수열합성 방법으로 소성하는 것은 140℃에서 30분 동안 실시하는 것을 특징으로 하는 가시광 감응 광촉매의 제조방법.Firing by the microwave hydrothermal synthesis method is a method for producing a visible light-sensitive photocatalyst, characterized in that carried out for 30 minutes at 140 ℃.
- 제 12항에 있어서,The method of claim 12,상기 Er(NO3)3·5H2O 수용액 은 4mol% 내지 5mol%로 하는 것을 특징으로 하는 가시광 감응 광촉매의 제조방법.The method of producing a visible light-sensitive photocatalyst, wherein the Er (NO 3 ) 3 .5H 2 O aqueous solution is 4 mol% to 5 mol%.
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