JP2020111476A - Method for producing visible light-responsive bismuth vanadate - Google Patents
Method for producing visible light-responsive bismuth vanadate Download PDFInfo
- Publication number
- JP2020111476A JP2020111476A JP2019001764A JP2019001764A JP2020111476A JP 2020111476 A JP2020111476 A JP 2020111476A JP 2019001764 A JP2019001764 A JP 2019001764A JP 2019001764 A JP2019001764 A JP 2019001764A JP 2020111476 A JP2020111476 A JP 2020111476A
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- bismuth vanadate
- compound
- reaction
- visible light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 46
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 44
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 16
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 15
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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 14
- 238000002834 transmittance Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000013032 photocatalytic reaction Methods 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 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 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 231100000507 endocrine disrupting Toxicity 0.000 description 2
- 229940011871 estrogen Drugs 0.000 description 2
- 239000000262 estrogen Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- -1 alum Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
Images
Abstract
Description
本発明は、可視光応答性バナジン酸ビスマスの製造方法に関する。 The present invention relates to a method for producing visible light-responsive bismuth vanadate.
現在、光触媒として広く活用されている酸化チタン（ＴｉＯ２）は、３．２ｅＶのバンドギャップを有し、波長が３８８ｎｍ以下の紫外光を利用するものである。しかし、紫外光は太陽光中に３〜５％程度しか含まれておらず、酸化チタンを使用した触媒反応では、太陽光の約９５％が利用できないことになる。 Titanium oxide (TiO 2 ) currently widely used as a photocatalyst has a band gap of 3.2 eV and utilizes ultraviolet light having a wavelength of 388 nm or less. However, ultraviolet light contains only about 3 to 5% of sunlight, which means that about 95% of sunlight cannot be used in the catalytic reaction using titanium oxide.
可視光応答性を示す光触媒として、バナジン酸ビスマス（ＢｉＶＯ４）が知られている（特許文献１）。正方晶構造のバナジン酸ビスマスは２．９ｅＶのバンドギャップを有し、単斜晶構造のバナジン酸ビスマスは２．４ｅＶのバンドギャップを有する（非特許文献１）。これは、前者が約４２８ｎｍ以下の波長の光を吸収するのに対し、後者が約５１７ｎｍ以下の波長の光を吸収することを意味する。単斜晶構造の方が正方晶構造よりも広い波長領域の光を吸収するため、光触媒効率が高くなる。酸化チタンと比較すると、約３．５倍もの太陽光エネルギーを吸収することができる。 Bismuth vanadate (BiVO 4 ) is known as a photocatalyst exhibiting visible light response (Patent Document 1). Bismuth vanadate having a tetragonal structure has a band gap of 2.9 eV, and bismuth vanadate having a monoclinic structure has a band gap of 2.4 eV (Non-Patent Document 1). This means that the former absorbs light with a wavelength of about 428 nm or less, while the latter absorbs light with a wavelength of about 517 nm or less. Since the monoclinic structure absorbs light in a wider wavelength range than the tetragonal structure, the photocatalytic efficiency is higher. Compared with titanium oxide, it can absorb about 3.5 times as much solar energy.
バナジン酸ビスマスの作製方法として、固相反応法や液相反応法が知られている。しかし、固相反応法を用いて作製されたバナジン酸ビスマス粉末は、光触媒反応の効率が低い。その原因として、固相反応法で得られる粉末の粒径が不均一であることが考えられている。 As a method for producing bismuth vanadate, a solid phase reaction method and a liquid phase reaction method are known. However, the bismuth vanadate powder produced by the solid-phase reaction method has low photocatalytic reaction efficiency. As a cause for this, it is considered that the particle size of the powder obtained by the solid phase reaction method is not uniform.
一方、液相反応法の一種である沈殿法を用いて、バナジン酸ビスマスを製造する方法が知られている（特許文献１）。具体的には、硝酸水溶液中で、尿素の存在下、メタバナジン酸アンモニウム（ＮＨ４ＶＯ３）と硝酸ビスマス五水和物（Ｂｉ（ＮＯ３）３・５Ｈ２Ｏ）とをモル比１：１で混合し、９０℃で加熱撹拌することにより、バナジン酸ビスマス粉末を得ている。得られたバナジン酸ビスマスが可視光応答性の光触媒活性を有し、内分泌攪乱物質であるノニルフェノール、ビスフェノールＡ又はエストロゲンを可視光下で分解できることも開示されている。しかしながら、短時間で単斜晶の粉末を得ることが難しく、また、使用する硝酸は劇物であり、保管取扱がきわめて難しいという問題がある。
On the other hand, a method for producing bismuth vanadate using a precipitation method, which is a type of liquid phase reaction method, is known (Patent Document 1). Specifically, an aqueous nitric acid solution in the presence of urea,
本発明は、光触媒効率が高いバナジン酸ビスマスを簡便に作製することを目的とする。 An object of the present invention is to easily produce bismuth vanadate with high photocatalytic efficiency.
本発明者らは、液相反応法によるバナジン酸ビスマスの製造方法について種々検討したところ、ビスマス原子１モルに対しバナジウム原子２モル以上となる量のバナジウム化合物をビスマス化合物と反応させることにより、硝酸水溶液を用いることなく、短時間で可視光応答性のバナジン酸ビスマスが得られることを見出し、本発明を完成した。 The present inventors have conducted various studies on a method for producing bismuth vanadate by a liquid phase reaction method. As a result, by reacting an amount of vanadium compound of 2 moles or more with 1 mole of bismuth atom with a bismuth compound, nitric acid The present invention has been completed by finding that visible light responsive bismuth vanadate can be obtained in a short time without using an aqueous solution.
すなわち、本発明は、水中で、ビスマス化合物と、ビスマス原子に対するバナジウム原子のモル比が２以上となる量のバナジウム化合物とを反応させる工程を含むバナジン酸ビスマスの製造方法に関する。 That is, the present invention relates to a method for producing bismuth vanadate, which comprises the step of reacting a bismuth compound with an amount of a vanadium compound in which the molar ratio of vanadium atom to bismuth atom is 2 or more in water.
バナジン酸ビスマスの結晶構造は単斜晶であることが好ましい。 The crystal structure of bismuth vanadate is preferably monoclinic.
ビスマス化合物が硝酸ビスマスであることが好ましい。 It is preferred that the bismuth compound is bismuth nitrate.
バナジウム化合物がメタバナジン酸アンモニウムであることが好ましい。 The vanadium compound is preferably ammonium metavanadate.
反応は６０〜９５℃で行うことが好ましい。 The reaction is preferably carried out at 60 to 95°C.
反応を尿素の存在下で行うことが好ましい。 It is preferred to carry out the reaction in the presence of urea.
反応時間は２時間以上であることが好ましい。 The reaction time is preferably 2 hours or more.
反応は硝酸の非存在下で行うことが好ましい。 The reaction is preferably carried out in the absence of nitric acid.
本発明では、ビスマス化合物と、ビスマス原子に対するバナジウム原子のモル比が２以上となる量のバナジウム化合物とを反応させるため、硝酸水溶液を用いることなく、可視光応答性のバナジン酸ビスマスを短時間で作製することができる。 In the present invention, the bismuth compound is reacted with the vanadium compound in an amount such that the molar ratio of the vanadium atom to the bismuth atom is 2 or more. Can be made.
本発明のバナジン酸ビスマスの製造方法は、水中で、ビスマス化合物と、ビスマス原子に対するバナジウム原子のモル比が２以上となる量のバナジウム化合物とを反応させる工程を含む。 The method for producing bismuth vanadate of the present invention includes a step of reacting a bismuth compound with an amount of the vanadium compound in which the molar ratio of vanadium atom to bismuth atom is 2 or more in water.
ビスマス原子に対するバナジウム原子のモル比（バナジウム原子のモル数／ビスマス原子のモル数）は、２以上であり、３以上がより好ましく、４以上がさらに好ましい。上限は特に限定されないが、１０以下が好ましく、５以下がより好ましい。２未満では、正方晶系結晶が生成しやすくなる傾向があり、２を超えると、少しずつ正方晶系の割合が減少し、単斜晶系に置き換わっていく傾向がある。 The molar ratio of vanadium atoms to bismuth atoms (the number of vanadium atoms/the number of bismuth atoms) is 2 or more, preferably 3 or more, and more preferably 4 or more. The upper limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less. When it is less than 2, tetragonal crystals tend to be easily generated, and when it exceeds 2, the proportion of tetragonal systems gradually decreases and monoclinic systems tend to be replaced.
ビスマス化合物としては、水に可溶な化合物であればよく、硝酸ビスマスが好ましい。 As the bismuth compound, any compound soluble in water may be used, and bismuth nitrate is preferable.
バナジウム化合物としては、水に可溶な化合物であればよく、取り扱いやすく、安価で毒性も低い点から、メタバナジン酸アンモニウムが好ましい。 As the vanadium compound, any compound that is soluble in water may be used, and ammonium metavanadate is preferable because it is easy to handle, inexpensive, and low in toxicity.
ビスマス化合物は、水１００重量部に対しビスマス原子換算で０．００１〜５モル使用することが好ましい。 The bismuth compound is preferably used in an amount of 0.001 to 5 mol in terms of bismuth atom based on 100 parts by weight of water.
バナジウム化合物とビスマス化合物の混合方法は特に限定されず、バナジウム化合物とビスマス化合物が入った反応容器に水を加えてもよく、水が入った反応容器にバナジウム化合物とビスマス化合物を加えてもよく、反応容器にバナジウム化合物の水溶液とビスマス化合物の水溶液とを加えてもよい。 The method for mixing the vanadium compound and the bismuth compound is not particularly limited, and water may be added to the reaction vessel containing the vanadium compound and the bismuth compound, or the vanadium compound and the bismuth compound may be added to the reaction vessel containing the water, An aqueous solution of vanadium compound and an aqueous solution of bismuth compound may be added to the reaction vessel.
本発明の製造方法では、反応系中に沈殿剤を存在させることが好ましい。沈殿剤としては特に限定されないが、尿素、ミョウバン、石灰乳等を挙げることができる。中でも、取扱いが容易で安価である点から、尿素が好ましい。
沈殿剤の量は、ビスマス化合物１モルに対し、０．００１〜１００モルが好ましい。
In the production method of the present invention, it is preferable that a precipitant is present in the reaction system. The precipitating agent is not particularly limited, and examples thereof include urea, alum, lime milk and the like. Of these, urea is preferable because it is easy to handle and inexpensive.
The amount of the precipitating agent is preferably 0.001 to 100 mol per 1 mol of the bismuth compound.
ビスマス化合物とバナジウム化合物は、両者を含む水溶液に、必要に応じて沈殿剤を混合し、必要に応じて加熱しながら撹拌する。その後、生成した沈殿物を回収し、洗浄、乾燥する。 The bismuth compound and the vanadium compound are mixed with an aqueous solution containing both of them, if necessary, with a precipitant, and stirred with heating as necessary. Then, the generated precipitate is collected, washed and dried.
反応温度は特に限定されないが、６０℃以上が好ましく、８０℃以上がより好ましく、９０℃以上がさらに好ましい。また、１００℃以下が好ましく、９８℃以下がより好ましく、９５℃以下がさらに好ましい。６０℃未満であると、尿素の加水分解が行われない傾向がある。また、１００℃を超えると、水が蒸発するおそれがある。 The reaction temperature is not particularly limited, but is preferably 60°C or higher, more preferably 80°C or higher, and further preferably 90°C or higher. Further, it is preferably 100°C or lower, more preferably 98°C or lower, and further preferably 95°C or lower. If it is lower than 60°C, hydrolysis of urea tends not to occur. If it exceeds 100°C, water may be evaporated.
反応時間は特に限定されないが、２時間以上が好ましく、３時間以上がより好ましく、４時間以上がさらに好ましい。また、１２時間以下が好ましく、１０時間以下がより好ましい。２時間未満であると、正方晶系結晶が高い割合で生成する傾向がある。一方、１２時間を超えると、単斜晶系が支配的に存在する、あるいは単斜晶系のみとなり、正方晶系が消滅しやすい傾向がある。 Although the reaction time is not particularly limited, it is preferably 2 hours or longer, more preferably 3 hours or longer, still more preferably 4 hours or longer. Further, it is preferably 12 hours or less, more preferably 10 hours or less. If it is less than 2 hours, a high proportion of tetragonal crystals tends to be generated. On the other hand, if it exceeds 12 hours, the monoclinic system is predominantly present or only the monoclinic system is present, and the tetragonal system tends to disappear.
本発明の製造方法では、硝酸を添加してもよい。硝酸の添加量は、水１００重量部に対して、３０重量部以下が好ましく、１０重量部以下がより好ましい。安全性かつ簡便性の観点から、硝酸を添加せずに、すなわち、硝酸の非存在下で、反応を行うことが最も好ましい。 In the manufacturing method of the present invention, nitric acid may be added. The addition amount of nitric acid is preferably 30 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of water. From the viewpoint of safety and convenience, it is most preferable to carry out the reaction without adding nitric acid, that is, in the absence of nitric acid.
生成するバナジン酸ビスマスは、単斜晶系結晶を含むことが好ましい。単斜晶系結晶と正方晶系結晶の混合物である場合は、重量比（単斜晶／正方晶）は、１００／１００以上であることが好ましく、１００／５０以上であることがより好ましく、１００／３３以上であることがさらに好ましい。 The resulting bismuth vanadate preferably contains monoclinic crystals. In the case of a mixture of monoclinic crystals and tetragonal crystals, the weight ratio (monoclinic/tetragonal) is preferably 100/100 or more, more preferably 100/50 or more, It is more preferably 100/33 or more.
本発明の製造方法によれば、単斜晶系結晶の割合が高いバナジン酸ビスマスを製造することができるので、可視光領域を含む幅広い波長領域の光を利用する光触媒反応に適用することができる。よって、可視光下でも、有害物質の分解、汚染された物質の浄化、水の分解等を高効率で行うことができ、例えば、内分泌攪乱物質であるノニルフェノール、ビスフェノールＡ、天然エストロゲン等で汚染された物質の浄化に応用できる。 According to the production method of the present invention, it is possible to produce bismuth vanadate with a high proportion of monoclinic crystals, and thus it can be applied to a photocatalytic reaction utilizing light in a wide wavelength range including a visible light range. .. Therefore, even under visible light, it is possible to decompose harmful substances, purify contaminated substances, and decompose water with high efficiency. For example, nonylphenol, bisphenol A, natural estrogen, etc., which are endocrine disruptors, are contaminated. It can be applied to the purification of substances.
有害物質の分解方法や汚染された物質の浄化方法としては、公知の方法を用いることができ、例えば、バナジン酸ビスマスを有害物質の水溶液に分散させ、光を照射しながら一定時間撹拌する方法が挙げられる。バナジン酸ビスマスは、濾別により除去・回収することができる。 As a method for decomposing harmful substances or a method for cleaning contaminated substances, known methods can be used, for example, a method of dispersing bismuth vanadate in an aqueous solution of harmful substances and stirring for a certain period of time while irradiating with light. Can be mentioned. Bismuth vanadate can be removed and recovered by filtration.
以下、本発明の実施例について説明するが、本発明は、以下の実施例に限定されない。
下記の実施例及び比較例で使用した材料及び調製したバナジン酸ビスマス粉末の評価方法を以下に示す。
Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.
The materials used in the following Examples and Comparative Examples and the evaluation method of the prepared bismuth vanadate powder are shown below.
＜Ｘ線回折（ＸＲＤ）測定＞
Ｘ線回折装置（ＲＩＮＴ２５００Ｖ、株式会社リガク製）を使用してバナジン酸ビスマス粉末の結晶性を評価した。
<X-ray diffraction (XRD) measurement>
The crystallinity of the bismuth vanadate powder was evaluated using an X-ray diffractometer (RINT2500V, manufactured by Rigaku Corporation).
＜光触媒反応評価＞
バナジン酸ビスマス粉末（０．２ｇ）をメチレンブルー溶液（８００μｌ）に加え、撹拌しながら太陽光シミュレーター装置（ＸＥＳ−３０１Ｓ＋ＥＬ−１００、株式会社三永電機製作所製）を用いて光（波長１００〜１４００ｎｍ）を１時間照射した。メチレンブルー溶液の上澄み３００μｌをガラス基板上に滴下し、分光器（大塚電子株式会社製）を用いて、波長２００〜８００ｎｍの光の透過率を測定した。水及びメチレンブルー溶液の透過率も測定した。
また、波長６６４ｎｍの光の透過率の測定結果をもとに、下記の方法により透過率の回復率を算出した。
回復率｛％｝＝（溶液の透過率／水の透過率）×１００
<Photocatalytic reaction evaluation>
Bismuth vanadate powder (0.2 g) was added to a methylene blue solution (800 μl), and light (
Further, the recovery rate of the transmittance was calculated by the following method based on the measurement result of the transmittance of the light having the wavelength of 664 nm.
Recovery rate {%}=(solution transmittance/water transmittance)×100
実施例１
硝酸ビスマス五水和物（５．８ｇ、１２ｍｍｏｌ）とメタバナジン酸アンモニウム（２．８ｇ、２４ｍｍｏｌ）をビーカー内で混合した上、超純水（１５０ｍｌ）と尿素（１０ｇ）を加え、９０℃、５００ｒｐｍで２時間加熱撹拌した。上澄みを捨てて、得られた沈殿物に超純水を加え５分間以上撹拌する作業を２回以上繰り返したのち、遠心分離機（３０００ｒｐｍ、１５分）を用いて沈殿物を回収した。１００℃で２時間乾燥し、粉末化した。
Example 1
Bismuth nitrate pentahydrate (5.8 g, 12 mmol) and ammonium metavanadate (2.8 g, 24 mmol) were mixed in a beaker, then ultrapure water (150 ml) and urea (10 g) were added, and 90° C., 500 rpm The mixture was heated and stirred for 2 hours. The supernatant was discarded, ultrapure water was added to the obtained precipitate, and the operation of stirring for 5 minutes or more was repeated twice or more, and then the precipitate was recovered using a centrifuge (3000 rpm, 15 minutes). It was dried at 100° C. for 2 hours and pulverized.
実施例２〜４
硝酸ビスマス五水和物（５．８ｇ、１２ｍｍｏｌ）に対し、メタバナジン酸アンモニウムをそれぞれ４．２ｇ（３６ｍｍｏｌ）、５．６ｇ（４８ｍｍｏｌ）、７．００ｇ（６０ｍｍｏｌ）用いた以外は、実施例１と同様にして沈殿物を得た。
Examples 2-4
Example 1 except that 4.2 g (36 mmol), 5.6 g (48 mmol), and 7.00 g (60 mmol) of ammonium metavanadate were used for bismuth nitrate pentahydrate (5.8 g, 12 mmol), respectively. A precipitate was obtained in the same manner.
比較例１
硝酸ビスマス五水和物（５．８ｇ、１２ｍｍｏｌ）に対し、メタバナジン酸アンモニウムを１．４ｇ（１２ｍｍｏｌ）用いた以外は、実施例１と同様にして沈殿物を得た。
Comparative Example 1
A precipitate was obtained in the same manner as in Example 1 except that 1.4 g (12 mmol) of ammonium metavanadate was used with respect to bismuth nitrate pentahydrate (5.8 g, 12 mmol).
実施例１〜４および比較例１で得られた各バナジン酸ビスマス粉末のＸＲＤの積分強度を図１に示す。比較例１（Ｖ原子とＢｉ原子のモル比が１）では、正方晶系結晶のピークが確認された。これに対し、実施例１、２及び４では、正方晶系結晶のピークがごくわずか確認される程度で、単斜晶系結晶が高い割合を占めることが確認された。Ｖ原子とＢｉ原子のモル比が４の実施例３では、正方晶系結晶のピークは見られず、単斜晶系結晶のピークのみが確認された。 FIG. 1 shows the integrated intensity of XRD of each bismuth vanadate powder obtained in Examples 1 to 4 and Comparative Example 1. In Comparative Example 1 (the molar ratio of V atom and Bi atom was 1), a peak of a tetragonal crystal was confirmed. On the other hand, in Examples 1, 2 and 4, it was confirmed that the monoclinic system crystals occupy a high proportion to the extent that the peaks of the tetragonal system crystals were confirmed only slightly. In Example 3 in which the molar ratio of V atom to Bi atom was 4, no peak of the tetragonal crystal was observed and only the peak of the monoclinic crystal was confirmed.
実施例１〜４および比較例１で得られた各バナジン酸ビスマス粉末の光触媒反応評価結果を図２に、透過率の回復率を図３に、それぞれ示す。
Ｖ原子とＢｉ原子のモル比が２以上で透過率の回復が確認された。特に、実施例４では透過率が約９８％にまで回復した。これは、単斜晶系結晶の比率が高いと可視光領域での光触媒反応を効率的に行えることを示している。
The photocatalytic reaction evaluation results of the bismuth vanadate powders obtained in Examples 1 to 4 and Comparative Example 1 are shown in FIG. 2, and the transmittance recovery rate is shown in FIG.
It was confirmed that the transmittance was recovered when the molar ratio of V atom and Bi atom was 2 or more. Particularly, in Example 4, the transmittance was recovered to about 98%. This indicates that the photocatalytic reaction in the visible light region can be efficiently performed when the ratio of monoclinic crystals is high.
比較例２
硝酸ビスマス五水和物（５．８ｇ、１２ｍｍｏｌ）とメタバナジン酸アンモニウム（１．４ｇ、１２ｍｍｏｌ）をビーカー内で混合した上、超純水（１５０ｍｌ）と尿素（１０ｇ）を加え、９０℃、５００ｒｐｍで、２時間、６時間又は１２時間加熱撹拌した。上澄みを捨てて、得られた沈殿物に超純水を加え５分間以上撹拌する作業を２回以上繰り返したのち、遠心分離機（３０００ｒｐｍ、１５分）を用いて沈殿物を回収した。１００℃で２時間乾燥し、粉末化した。
Comparative example 2
After mixing bismuth nitrate pentahydrate (5.8 g, 12 mmol) and ammonium metavanadate (1.4 g, 12 mmol) in a beaker, ultrapure water (150 ml) and urea (10 g) were added, and 90°C, 500 rpm Then, the mixture was heated and stirred for 2 hours, 6 hours, or 12 hours. The supernatant was discarded, ultrapure water was added to the obtained precipitate, and the operation of stirring for 5 minutes or more was repeated twice or more, and then the precipitate was recovered using a centrifuge (3000 rpm, 15 minutes). It was dried at 100° C. for 2 hours and pulverized.
バナジン酸ビスマス粉末のＸＲＤの積分強度を図４に示す。反応時間が２時間では、正方晶系結晶のピークのみが確認された。６時間では正方晶系結晶と単斜晶系結晶の混合物が得られ、１２時間では正方晶系結晶の割合はかなり低くなった。 The integrated intensity of XRD of the bismuth vanadate powder is shown in FIG. When the reaction time was 2 hours, only the peak of the tetragonal crystal was confirmed. A mixture of tetragonal crystals and monoclinic crystals was obtained in 6 hours, and the proportion of tetragonal crystals was considerably low in 12 hours.
各バナジン酸ビスマス粉末の光触媒反応評価結果を図５に、この結果をもとに算出した透過率の回復率を図６に、それぞれ示す。
Ｖ原子とＢｉ原子のモル比が１である場合、１２時間反応させても透過率が９０％近くまでしか回復しないことが確認された。
The photocatalytic reaction evaluation results of each bismuth vanadate powder are shown in FIG. 5, and the transmittance recovery rates calculated based on these results are shown in FIG.
It was confirmed that when the molar ratio of V atom and Bi atom was 1, the transmittance was recovered to almost 90% even after reacting for 12 hours.
本発明によれば、可視光応答性のバナジン酸ビスマスが簡便に得られるため、可視光下での有機物質の分解手段、例えば、内分泌攪乱物質等の環境汚染物質を分解・浄化する手段等に応用することができる。 According to the present invention, since visible light responsive bismuth vanadate can be easily obtained, it can be used as a means for decomposing organic substances under visible light, for example, a means for decomposing/purifying environmental pollutants such as endocrine disrupting substances. It can be applied.
Claims (8)
The production method according to claim 1, wherein the reaction is carried out in the absence of nitric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019001764A JP7292703B2 (en) | 2019-01-09 | 2019-01-09 | Method for producing visible-light-responsive bismuth vanadate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019001764A JP7292703B2 (en) | 2019-01-09 | 2019-01-09 | Method for producing visible-light-responsive bismuth vanadate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2020111476A true JP2020111476A (en) | 2020-07-27 |
| JP7292703B2 JP7292703B2 (en) | 2023-06-19 |
Family
ID=71668138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019001764A Active JP7292703B2 (en) | 2019-01-09 | 2019-01-09 | Method for producing visible-light-responsive bismuth vanadate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7292703B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020080150A (en) * | 2018-11-13 | 2020-05-28 | 株式会社すなおネット | Commodity information management system and service information management system |
| CN115779942A (en) * | 2022-08-29 | 2023-03-14 | 湖南大学 | Modified fern-shaped bismuth vanadate photocatalytic nano material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58156508A (en) * | 1982-02-08 | 1983-09-17 | ユニオン・オイル・コンパニ−・オブ・カリフオルニア | Oxidizing catalyst for hydrogen sulfide and its oxidation method |
| JPS5957915A (en) * | 1982-09-27 | 1984-04-03 | Res Dev Corp Of Japan | Amorphous bismuth-vanadium compound material and its manufacture |
| JP2004024936A (en) * | 2002-06-21 | 2004-01-29 | Japan Science & Technology Corp | New synthetic method for fine powder of visible light-responsive bismuth vanadate, photocatalyst of fine powder of new visible light-responsive bismuth vanadate and cleaning method using the same |
| JP2004202335A (en) * | 2002-12-25 | 2004-07-22 | Sk Kaken Co Ltd | Photocatalyst compound powder having visible light responsiveness |
| US20090226354A1 (en) * | 2008-03-04 | 2009-09-10 | Worleyparsons Group, Inc. | Process for Catalytic Tail Gas Incineration |
| CN102963930A (en) * | 2012-11-09 | 2013-03-13 | 陕西科技大学 | Method for preparing BiVO4 with photocatalytic performance under visible lights |
| WO2014136783A1 (en) * | 2013-03-07 | 2014-09-12 | 学校法人東京理科大学 | Bismuth-vanadate-laminate manufacturing method and bismuth-vanadate laminate |
-
2019
- 2019-01-09 JP JP2019001764A patent/JP7292703B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58156508A (en) * | 1982-02-08 | 1983-09-17 | ユニオン・オイル・コンパニ−・オブ・カリフオルニア | Oxidizing catalyst for hydrogen sulfide and its oxidation method |
| JPS5957915A (en) * | 1982-09-27 | 1984-04-03 | Res Dev Corp Of Japan | Amorphous bismuth-vanadium compound material and its manufacture |
| JP2004024936A (en) * | 2002-06-21 | 2004-01-29 | Japan Science & Technology Corp | New synthetic method for fine powder of visible light-responsive bismuth vanadate, photocatalyst of fine powder of new visible light-responsive bismuth vanadate and cleaning method using the same |
| JP2004202335A (en) * | 2002-12-25 | 2004-07-22 | Sk Kaken Co Ltd | Photocatalyst compound powder having visible light responsiveness |
| US20090226354A1 (en) * | 2008-03-04 | 2009-09-10 | Worleyparsons Group, Inc. | Process for Catalytic Tail Gas Incineration |
| CN102963930A (en) * | 2012-11-09 | 2013-03-13 | 陕西科技大学 | Method for preparing BiVO4 with photocatalytic performance under visible lights |
| WO2014136783A1 (en) * | 2013-03-07 | 2014-09-12 | 学校法人東京理科大学 | Bismuth-vanadate-laminate manufacturing method and bismuth-vanadate laminate |
Non-Patent Citations (1)
| Title |
|---|
| OHATA Y. ET AL., 第65回応用物理学会春季学術講演会講演予稿集, JPN7022005578, 17 March 2018 (2018-03-17), JP, pages 5 - 27, ISSN: 0004931194 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020080150A (en) * | 2018-11-13 | 2020-05-28 | 株式会社すなおネット | Commodity information management system and service information management system |
| CN115779942A (en) * | 2022-08-29 | 2023-03-14 | 湖南大学 | Modified fern-shaped bismuth vanadate photocatalytic nano material and preparation method and application thereof |
| CN115779942B (en) * | 2022-08-29 | 2024-01-26 | 湖南大学 | Modified fern-shaped bismuth vanadate photocatalytic nanomaterial as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7292703B2 (en) | 2023-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Efficient methylene blue removal over hydrothermally synthesized starlike BiVO4 | |
| US7763149B2 (en) | Solar photocatalysis using transition-metal oxides combining d0 and d6 electron configurations | |
| WO2005014170A1 (en) | Photocatalyst material being activated by visible light, raw material for the same and method for producing the same | |
| JP4587485B2 (en) | Method for producing brookite type titanium dioxide | |
| CN102351242A (en) | Solvent-thermal method for preparing single-phase bismuth titanate Bi2Ti2O7 | |
| Vega et al. | Visible light photocatalytic activity of sol–gel Ni-doped TiO 2 on p-arsanilic acid degradation | |
| JP6186246B2 (en) | Method for producing crystalline titanium oxide and method for regenerating denitration catalyst | |
| JP7292703B2 (en) | Method for producing visible-light-responsive bismuth vanadate | |
| TW201741025A (en) | Bimetal oxysulfide solid-solution catalyst and manufacturing method thereof, method for carbon dioxide reduction, method for heavy metal reduction, and method for hydrogenation of organic compounds | |
| EP1492729B1 (en) | Method for preparing a photocatalyst containing titanium dioxide | |
| JP2017081812A (en) | Manganese-zirconium-based composite oxide and manufacturing method therefor and application thereof | |
| Phiankoh et al. | Effect of pH on crystal structure and morphology of hydrothermally-synthesized BiVO4 | |
| KR100840750B1 (en) | Titanium oxide mixture powder solution for photocatalystic | |
| CN104607176A (en) | Preparation method of nano bismuth tantalite photocatalyst and application of nano bismuth tantalite photocatalyst to photocatalytic degradation of organic pollutants | |
| KR20120095855A (en) | Copper ion-modified titanium oxide and process for producing the same, and photocatalyst | |
| EP4282523A1 (en) | Denitration catalyst and method for producing same | |
| JP5050182B2 (en) | Catalyst for amide dehydration reaction and method for producing nitrile using the same | |
| Febiyanto et al. | Facile synthesis of Ag3PO4 photocatalyst with varied ammonia concentration and its photocatalytic activities for dye removal | |
| JPS61136902A (en) | Manufacture of chlorine | |
| RU2435733C1 (en) | Method of producing photocatalytic nanocomposite containing titanium dioxide | |
| JP5356841B2 (en) | Method for treating aqueous solution containing ammonia | |
| CN104998661B (en) | Preparation method for visible light photocatalyst SnO2/ZnS nanosphere composite material | |
| KR20060128465A (en) | Nitrogen fixation at vegetable caused by titanium oxide mixture powder photo catalyst and utilization | |
| Putta et al. | Characterization and activity of visible-light driven TiO2 photocatalyst doped with tungsten | |
| JP2023158859A (en) | Visible light-responsive photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210804 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220531 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220614 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220804 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20221129 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230119 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230509 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230531 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7292703 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |