JP2015003840A - BiVO4 PARTICLE AND PRODUCTION METHOD THEREOF - Google Patents
BiVO4 PARTICLE AND PRODUCTION METHOD THEREOF Download PDFInfo
- Publication number
- JP2015003840A JP2015003840A JP2013129216A JP2013129216A JP2015003840A JP 2015003840 A JP2015003840 A JP 2015003840A JP 2013129216 A JP2013129216 A JP 2013129216A JP 2013129216 A JP2013129216 A JP 2013129216A JP 2015003840 A JP2015003840 A JP 2015003840A
- Authority
- JP
- Japan
- Prior art keywords
- bivo
- particles
- bragg angle
- plane
- water
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 229910002915 BiVO4 Inorganic materials 0.000 title 1
- 239000011941 photocatalyst Substances 0.000 claims abstract description 16
- 239000011164 primary particle Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 2
- 150000001622 bismuth compounds Chemical class 0.000 claims 1
- 238000012916 structural analysis Methods 0.000 claims 1
- 150000003682 vanadium compounds Chemical class 0.000 claims 1
- 238000002441 X-ray diffraction Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 13
- 229910052797 bismuth Inorganic materials 0.000 description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052720 vanadium Inorganic materials 0.000 description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 9
- 229910001451 bismuth ion Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910001456 vanadium ion Inorganic materials 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003746 solid phase reaction Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 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 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- 239000001358 L(+)-tartaric acid Substances 0.000 description 1
- 235000011002 L(+)-tartaric acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N L-(+)-Tartaric acid Natural products OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- -1 bismuth iodide Bismuth fluoride Chemical compound 0.000 description 1
- JAONZGLTYYUPCT-UHFFFAOYSA-K bismuth subgallate Chemical compound OC(=O)C1=CC(O)=C2O[Bi](O)OC2=C1 JAONZGLTYYUPCT-UHFFFAOYSA-K 0.000 description 1
- 229960000199 bismuth subgallate Drugs 0.000 description 1
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- ZOYIPGHJSALYPY-UHFFFAOYSA-K vanadium(iii) bromide Chemical compound [V+3].[Br-].[Br-].[Br-] ZOYIPGHJSALYPY-UHFFFAOYSA-K 0.000 description 1
- 238000012982 x-ray structure analysis Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、ＢｉＶＯ４粒子とその製造方法に関する。 The present invention relates to BiVO 4 particles and a method for producing the same.
可視光応答型光触媒は、太陽光に多く含まれる可視光線を利用可能な光触媒として、有機物の光分解や、水の光分解による水素製造への応用に期待されている。中でも、水素製造を目指した水分解用光触媒は、再生可能エネルギーを利用した水素製造方法として注目されているが、その高活性化の要求が年々高まっている。 Visible light responsive photocatalysts are expected to be applied to hydrogen production by photolysis of organic matter and water by photolysis as a photocatalyst that can use visible light contained in a large amount of sunlight. Among them, water splitting photocatalysts aimed at hydrogen production are attracting attention as a method for producing hydrogen using renewable energy, but the demand for higher activation is increasing year by year.
可視光応答性がある水分解用光触媒として、バナジン酸ビスマス（ＢｉＶＯ４）は、水からの酸素発生能が非常に高いことが知られており、水素発生用光触媒と組合せたＺスキーム型システムにおいて、高い水分解反応におけるエネルギー変換効率が得られることが知られている（Ｓａｓａｋｉら、Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．Ｃ １７５３６〜１７ ５４２ページ、２００９年（非特許文献１））。従来、ＢｉＶＯ４は、固相反応法や酸エージング法により作製されることが知られている。特開２００４−２４９３６号公報（特許文献１）には、尿素の存在下でＮＨ４ＶＯ３とＢｉ（ＮＯ３）３を反応させる均一沈殿法（酸エージング法）によるＢｉＶＯ４の製造方法が記載されている。また、Ｉｗａｓｅら、Ｊ．Ｍａｔｅｒ．Ｃｈｅｍ．７３５６ページ、２０１０年（非特許文献２）には、固相反応法によるＢｉＶＯ４の製造方法が記載されている。 As a photocatalyst for water splitting with visible light responsiveness, bismuth vanadate (BiVO 4 ) is known to have a very high ability to generate oxygen from water. In a Z-scheme system combined with a photocatalyst for hydrogen generation, It is known that energy conversion efficiency in a high water splitting reaction can be obtained (Sasaki et al., J. Phys. Chem. C 17536-17542, 2009 (Non-patent Document 1)). Conventionally, it is known that BiVO 4 is produced by a solid phase reaction method or an acid aging method. Japanese Unexamined Patent Application Publication No. 2004-24936 (Patent Document 1) describes a method for producing BiVO 4 by a homogeneous precipitation method (acid aging method) in which NH 4 VO 3 and Bi (NO 3 ) 3 are reacted in the presence of urea. Has been. Iwase et al. Mater. Chem. On page 7356, 2010 (Non-Patent Document 2), a method for producing BiVO 4 by a solid phase reaction method is described.
更なる高活性化の手法として、比表面積の増大が求められているが、高い反応活性を有しつつ比表面積の大きいＢｉＶＯ４粒子の開発は現状困難であり、さらに、水分解反応に対する高い反応活性を実現可能な結晶面に関する知見はほとんど得られていない。 As a method for further increasing the activity, an increase in specific surface area is required. However, it is difficult to develop BiVO 4 particles having a high specific activity and a large specific surface area. Little knowledge about crystal planes that can achieve activity has been obtained.
そこで、本発明は、このような課題に鑑みてなされたものであり、その目的は、大きい比表面積、すなわち、微細な一次粒子径と、高い水分解反応活性と相関のある結晶面を有するＢｉＶＯ４粒子を提供することにある。 Therefore, the present invention has been made in view of such problems, and its purpose is to provide a large specific surface area, that is, a BiVO having a crystal face correlated with a high primary water particle reaction activity and a fine primary particle diameter. To provide 4 particles.
本発明のＢｉＶＯ４粒子は、一次粒子径が１００ｎｍ以下であり、Ｘ線回折スペクトルにより測定される結晶構造が単斜晶シーライト構造であり、かつ、（１０１）面におけるブラッグ角２θ＝１８．７°のピークと（０１１）面におけるブラッグ角２θ＝１９．０°のピークの中間であるブラッグ角２θ＝１８．８°のＸ線強度Ｉ（２θ＝１８．８°）と、（０１１）面におけるブラッグ角２θ＝１９．０°のＸ線強度Ｉ（２θ＝１９．０°）のＸ線強度比Ａ（Ｉ（２θ＝１８．８°）／Ｉ（２θ＝１９．０°））が０．８３以下であることを特徴とする。 The BiVO 4 particles of the present invention have a primary particle size of 100 nm or less, a crystal structure measured by an X-ray diffraction spectrum is a monoclinic celite structure, and a Bragg angle 2θ = 18.18 in the (101) plane. X-ray intensity I (2θ = 18.8 °) with a Bragg angle 2θ = 18.8 °, which is the middle between the peak at 7 ° and the Bragg angle 2θ = 19.0 ° in the (011) plane, and (011) X-ray intensity ratio A (I (2θ = 18.8 °) / I (2θ = 19.0 °)) of X-ray intensity I (2θ = 19.0 °) at a Bragg angle 2θ = 19.0 ° in the plane Is 0.83 or less.
本発明によるＢｉＶＯ４粒子によれば、可視光照射下での高い光触媒活性の発現が可能となる。 According to the BiVO 4 particles of the present invention, high photocatalytic activity can be expressed under visible light irradiation.
ＢｉＶＯ ４ 粒子のＸ線回折スペクトルによるピーク
本発明におけるＢｉＶＯ４粒子は、微細な一次粒子径と、高い反応活性と相関のある結晶面を有するという特徴を有する。
BiVO 4 particles at the peak <br/> present invention by X-ray diffraction spectrum of BiVO 4 particles have a primary particle size fine, a feature of having a crystal plane having a correlation with high reaction activity.
従来のＢｉＶＯ４粒子では、Ｘ線構造回折において、（１０１）面におけるブラッグ角２θ＝１８．７の回折ピークと（０１１）面におけるブラッグ角２θ＝１９．０°の回折ピークがそれぞれ独立のピークではなく、単一ピークとして観測されることが知られている。また、（２００）面におけるブラッグ角２θ＝３４．５の回折ピークと（０２０）面におけるブラッグ角２θ＝３５．２°の回折ピークも、それぞれ独立のピークではなく単一ピークとして得られる傾向であることが知られていた。また、このようなＢｉＶＯ４粒子における光触媒活性に及ぼす結晶面依存性に関しても、全く知見がなかった。 In the conventional BiVO 4 particle, in the X-ray structure diffraction, the diffraction peak with the Bragg angle 2θ = 18.7 on the (101) plane and the diffraction peak with the Bragg angle 2θ = 19.0 ° on the (011) plane are independent peaks. Instead, it is known to be observed as a single peak. Also, the diffraction peak with a Bragg angle 2θ = 34.5 in the (200) plane and the diffraction peak with a Bragg angle 2θ = 35.2 ° in the (020) plane tend to be obtained as single peaks rather than as independent peaks. It was known that there was. Moreover, there was no knowledge about the crystal plane dependency on the photocatalytic activity in such BiVO 4 particles.
本発明者らは、本発明のＢｉＶＯ４粒子において、微細な一次粒子径を有し、かつ、Ｘ線構造回折における（１０１）面におけるブラッグ角２θ＝１８．７°のピークと、（０１１）面におけるブラッグ角２θ＝１９．０°のピークが、単一のピークではなく、それぞれ独立して観測されることが、ＢｉＶＯ４粒子における高い光触媒活性の発現に必要であることを見出した。ここで、本発明において、（１０１）面におけるブラッグ角２θ＝１８．７°のピークと、（０１１）面におけるブラッグ角２θ＝１９．０°のピークがそれぞれ独立して観測されるとは、すなわち、（１０１）面におけるブラッグ角２θ＝１８．７°のピークと、（０１１）面におけるブラッグ角２θ＝１９．０°のピークの中間であるブラッグ角２θ＝１８．８°のＸ線強度Ｉ（２θ＝１８．８°）を（０１１）面におけるブラッグ角２θ＝１９．０°のＸ線強度Ｉ（２θ＝１９．０°）で割って得られるＸ線強度比Ａが０．８３以下であることを満たすことである。つまり、式で示すと以下のようになる。
Ａ＝Ｉ（２θ＝１８．８°）／Ｉ（２θ＝１９．０°）≦０．８３
In the BiVO 4 particles of the present invention, the present inventors have a fine primary particle diameter and a peak at a Bragg angle 2θ = 18.7 ° in the (101) plane in X-ray structural diffraction, and (011) It was found that it is necessary for the expression of high photocatalytic activity in BiVO 4 particles that the peak at the Bragg angle 2θ = 19.0 ° in the plane is not a single peak but is observed independently. Here, in the present invention, the peak of the Bragg angle 2θ = 18.7 ° in the (101) plane and the peak of the Bragg angle 2θ = 19.0 ° in the (011) plane are observed independently. That is, the X-ray intensity of the Bragg angle 2θ = 18.8 °, which is the middle between the peak of the Bragg angle 2θ = 18.7 ° in the (101) plane and the peak of the Bragg angle 2θ = 19.0 ° in the (011) plane. The X-ray intensity ratio A obtained by dividing I (2θ = 18.8 °) by the X-ray intensity I (2θ = 19.0 °) at the Bragg angle 2θ = 19.0 ° in the (011) plane is 0.83. Satisfying that: In other words, this is expressed as follows:
A = I (2θ = 18.8 °) / I (2θ = 19.0 °) ≦ 0.83
Ｘ線構造回折における（１０１）面におけるブラッグ角２θ＝１８．７°のピークと、（０１１）面におけるブラッグ角２θ＝１９．０°のピークが、単一のピークではなく、それぞれ独立して観測されることが、ＢｉＶＯ４粒子における高い光触媒活性の発現に必要であることを見出した。 The peak of the Bragg angle 2θ = 18.7 ° in the (101) plane and the peak of the Bragg angle 2θ = 19.0 ° in the (011) plane in X-ray structural diffraction are not a single peak, but are independent of each other. It was found that what is observed is necessary for the development of high photocatalytic activity in BiVO 4 particles.
本発明のＢｉＶＯ４粒子のＸ線構造回折における（１０１）面におけるブラッグ角２θ＝１８．７°と、（０１１）面におけるブラッグ角２θ＝１９．０°におけるＸ線強度の概略図を図１に示す。 FIG. 1 is a schematic diagram of the X-ray intensity at the Bragg angle 2θ = 18.7 ° in the (101) plane and the Bragg angle 2θ = 19.0 ° in the (011) plane in the X-ray structure diffraction of BiVO 4 particles of the present invention. Shown in
また、本発明のＢｉＶＯ４粒子においては、（２００）面における２θ＝３４．５°のピークと、（０２０）面におけるブラッグ角２θ＝３５．２°のピークがそれぞれ独立して観測されることが好ましい。ここで、本発明において、（２００）面における２θ＝３４．５°のピークと、（０２０）面におけるブラッグ角２θ＝３５．２°のピークがそれぞれ独立して観測されるとは、すなわち、これらのブラッグ角の中間の角度である２θ＝３４．８５°でのＸ線強度Ｉ（２θ＝３４．８５°）を（２００）面におけるブラッグ角２θ＝３４．５°のＸ線強度Ｉ（２θ＝３４．５°）で割って得られるＸ線強度比Ｂが０．５以下であることを満たすことである。つまり、式で示すと以下のようになる。
Ｂ＝Ｉ（２θ＝３４．８５°）／Ｉ（２θ＝３４．５°）≦０．５
In the BiVO 4 particles of the present invention, the peak at 2θ = 34.5 ° in the (200) plane and the peak at the Bragg angle 2θ = 35.2 ° in the (020) plane are observed independently. Is preferred. Here, in the present invention, the 2θ = 34.5 ° peak in the (200) plane and the Bragg angle 2θ = 35.2 ° peak in the (020) plane are observed independently, that is, The X-ray intensity I (2θ = 34.85 °) at 2θ = 34.85 °, which is an intermediate angle between these Bragg angles, is changed to the X-ray intensity I (2θ = 34.5 ° in the (200) plane) ( 2θ = 34.5 °) and satisfying that the X-ray intensity ratio B obtained by dividing by 2) is 0.5 or less. In other words, this is expressed as follows:
B = I (2θ = 34.85 °) / I (2θ = 34.5 °) ≦ 0.5
本発明のＸ線構造回折における（２００）面における２θ＝３４．５°と、（０２０）面におけるブラッグ角２θ＝３５．２°のＸ線強度の概略図を図２に示す。 FIG. 2 shows a schematic diagram of the X-ray intensity of 2θ = 34.5 ° in the (200) plane and the Bragg angle 2θ = 35.2 ° in the (020) plane in the X-ray structure diffraction of the present invention.
本発明のＢｉＶＯ４粒子は、このようなＸ線回折特性を有することで、良好に発達した特定の結晶面を有すると考えられる。また、この発達した結晶面の表面が、光触媒による酸化還元反応サイトとして機能することで、迅速に光触媒反応が進行すると考えられる。よって、本発明のＢｉＶＯ４粒子では、可視光照射下での高い光触媒活性の発現が可能であると考えている。 The BiVO 4 particles of the present invention are considered to have specific crystal planes that are well developed by having such X-ray diffraction characteristics. Further, it is considered that the photocatalytic reaction proceeds rapidly by the surface of the developed crystal plane functioning as a redox reaction site by the photocatalyst. Therefore, it is considered that the BiVO 4 particles of the present invention can exhibit high photocatalytic activity under visible light irradiation.
本発明のＢｉＶＯ４粒子のＸ線回折スペクトルの測定方法としては、例えば、Ｘ線回折装置（ＰＡＮａｌｙｔｉｃａｌ製）を用いて、Ｘ線管の運転条件が、２５℃の温度条件で、印加電圧４５ｋＶ、電流２００ｍＡであり、ブラッグ角２θ＝１０°〜６０°の範囲を、２θのスキャン速度が毎分１．０〜５．０°で、０．０２〜０．１°間隔で測定することで可能となる。 As a method for measuring the X-ray diffraction spectrum of BiVO 4 particles of the present invention, for example, using an X-ray diffractometer (manufactured by PANalytical), the operating condition of the X-ray tube is 25 ° C., the applied voltage is 45 kV, Current is 200 mA, and the Bragg angle 2θ = 10 ° -60 ° can be measured at 0.02-0.1 ° intervals with a 2θ scan rate of 1.0-5.0 ° per minute. It becomes.
ＢｉＶＯ ４ の一次粒子径
本発明のＢｉＶＯ４粒子は、微細な一次粒子径を有し、好ましくは、１００ｎｍ以下の一次粒子径であり、さらに好ましくは８０ｎｍ以下である。このように微細な一次粒子径を有することで、高い比表面積となり、分解対象物質との接触面積が増加し、光触媒活性の向上が期待できるようになる。ＢｉＶＯ４粒子における一次粒子径の評価手法としては、例えば、走査型電子顕微鏡（株式会社日立製作所製、“Ｓ−４１００” 、以下、ＳＥＭ）を用い、倍率４００００倍で観察した際の結晶粒子５０個の円形近似にて求めた直径の平均値で定義することが可能である。
BiVO 4 particles of the primary particle size <br/> present invention BiVO 4 has a fine primary particle size, or preferably less primary particle size 100 nm, still more preferably 80nm or less. By having such a fine primary particle size, a high specific surface area is obtained, the contact area with the substance to be decomposed is increased, and an improvement in photocatalytic activity can be expected. As an evaluation method of the primary particle diameter of BiVO 4 particles, for example, a scanning electron microscope (manufactured by Hitachi, Ltd., “S-4100”, hereinafter referred to as SEM) is used, and the crystal particles 50 are observed at a magnification of 40000 times. It is possible to define the average value of the diameters obtained by round approximation.
以上のように、本発明のＢｉＶＯ４粒子は、上記に示すＸ線回折スペクトルによる（１０１）面におけるブラッグ角２θ＝１８．７°のピークと、（０１１）面におけるブラッグ角２θ＝１９．０°のピークのそれぞれ独立したピークと、ＳＥＭによる微細な一次粒子形状を両立することで、高い光触媒活性の発現が可能となる。 As described above, the BiVO 4 particles of the present invention have a Bragg angle 2θ = 18.7 ° peak in the (101) plane and a Bragg angle 2θ = 19.0 in the (011) plane according to the X-ray diffraction spectrum shown above. High photocatalytic activity can be achieved by satisfying both the independent peak of ° and the fine primary particle shape by SEM.
ＢｉＶＯ ４ 粒子の製造方法
本発明におけるＢｉＶＯ４粒子の製造方法としては、固相反応法などの乾式反応法や、酸エージング法、ゾル-ゲル法、錯体重合法、水熱反応法、均一沈殿法等の湿式反応法が利用可能である。例えば、固相反応法による作製方法としては、酸化ビスマスと酸化バナジウムを原料として混合し、６００℃以上での焼成を経てＢｉＶＯ４粒子を得る。また、湿式反応法の１つである酸エージング法による作製方法としては、酸化ビスマスと酸化バナジウムを原料として、酢酸または硝酸を含む水溶液に添加後、溶解させ、４００℃以上の焼成により、結晶化させる方法がある。本発明のＢｉＶＯ４粒子の製造方法としては、特に制限は無いが、以下の方法が好ましく利用できる。
As a method for producing BiVO 4 particles in the production process <br/> present invention BiVO 4 particles, solid or phase reaction method a dry reaction method, such as, acid aging method, a sol - gel method, complex polymerization method, a hydrothermal reaction method A wet reaction method such as a uniform precipitation method can be used. For example, as a production method by a solid phase reaction method, BiVO 4 particles are obtained by mixing bismuth oxide and vanadium oxide as raw materials and firing at 600 ° C. or higher. In addition, as a manufacturing method by an acid aging method, which is one of wet reaction methods, bismuth oxide and vanadium oxide are added as raw materials to an aqueous solution containing acetic acid or nitric acid, dissolved, and then crystallized by baking at 400 ° C. or higher. There is a way to make it. As a method for producing BiVO 4 particles of the present invention is not particularly limited, the following method can be preferably utilized.
ビスマスイオンおよびバナジウムイオンを含む水溶液を用いた粒子の製造
本発明におけるＢｉＶＯ４粒子の製造方法として、ビスマスイオン及びバナジウムイオンを含む水溶液を用いた熱分解法（水溶液熱分解法）を好ましく用いることが可能である。水溶液熱分解法とは、ＢｉＶＯ４前駆体を原料として用い、このＢｉＶＯ４前駆体を含む水溶液を加熱することで、溶媒である水の蒸発に伴い、ＢｉＶＯ４前駆体同士の脱水重縮合反応を起こす方法である。金属アルコキシドや塩化物等を用いるゾル‐ゲル法では、ＢｉＶＯ４前駆体同士の加水分解による金属水酸化物の生成と、これらの脱水重縮合が速やかに起こることで、結晶核が粗大化しやすい。これに対して、この水溶液熱分解法では、加水分解反応が緩やかなＢｉＶＯ４前駆体を原料として用いることで、水への安定な溶解が可能となる。また、このＢｉＶＯ４前駆体を含む水溶液を加熱して、溶媒である水が蒸発することに伴い、ＢｉＶＯ４前駆体同士の脱水重縮合反応が緩やかに起こる。これにより、熱分解時の結晶核の生成速度が遅くなり、結果的に結晶核の微細化が可能となる。
Production of particles using aqueous solution containing bismuth ions and vanadium ions As a method for producing BiVO 4 particles in the present invention, a thermal decomposition method (aqueous solution thermal decomposition method) using an aqueous solution containing bismuth ions and vanadium ions is used. It can be preferably used. The aqueous solution pyrolysis method uses a BiVO 4 precursor as a raw material, and heats an aqueous solution containing this BiVO 4 precursor to cause dehydration polycondensation reaction between the BiVO 4 precursors with the evaporation of water as a solvent. It is a way to wake up. In the sol-gel method using a metal alkoxide, a chloride, or the like, the crystal nucleus is likely to be coarsened due to the generation of metal hydroxide by hydrolysis of BiVO 4 precursors and the rapid dehydration polycondensation thereof. On the other hand, in this aqueous solution thermal decomposition method, by using a BiVO 4 precursor, which has a mild hydrolysis reaction, as a raw material, stable dissolution in water becomes possible. Further, when the aqueous solution containing the BiVO 4 precursor is heated to evaporate water as the solvent, the dehydration polycondensation reaction between the BiVO 4 precursors occurs gradually. This slows down the generation rate of crystal nuclei during pyrolysis, and as a result, miniaturization of crystal nuclei becomes possible.
本発明において、従来難水溶性であるビスマス塩やバナジウム塩を水溶化させる方法として、原料としてビスマスを含む化合物やバナジウムを含む化合物に、錯化剤を添加することが好ましい。ビスマスイオンやバナジウムイオンに錯化剤を配位させ、水溶性ビスマス錯体及び水溶性バナジウム錯体を形成することで、水への安定な溶解が可能となり、加水分解を抑制させることが好ましい。 In the present invention, it is preferable to add a complexing agent to a compound containing bismuth or a compound containing vanadium as a raw material as a method for water-solubilizing a bismuth salt or vanadium salt that has been conventionally poorly water-soluble. By coordinating a complexing agent to bismuth ions and vanadium ions to form a water-soluble bismuth complex and a water-soluble vanadium complex, it is possible to achieve stable dissolution in water and to suppress hydrolysis.
ビスマスを含む化合物としては、水溶性であり、加熱結晶化の際に、残渣としてアニオン成分が残らないものであればよく、例えば、硝酸ビスマス、酢酸ビスマス、臭化ビスマス、塩化ビスマス、よう化ビスマス、フッ化ビスマス、クエン酸ビスマス、水酸化ビスマス、次没食子酸ビスマス等が好ましく用いられ、より好ましくは、硝酸ビスマスが用いられる。また、バナジウムを含む化合物としては、水溶性であり、加熱結晶化の際に、残渣としてアニオン成分が残らないものであればよく、例えば、バナジン酸アンモニウム、塩化バナジウム、臭化バナジウム、フッ化バナジウム、等が用いられ、より好ましくは、バナジン酸アンモニウムが用いられる。 The bismuth-containing compound may be any compound that is water-soluble and does not leave an anionic component as a residue during heat crystallization. For example, bismuth nitrate, bismuth acetate, bismuth bromide, bismuth chloride, bismuth iodide Bismuth fluoride, bismuth citrate, bismuth hydroxide, bismuth subgallate and the like are preferably used, and bismuth nitrate is more preferably used. The vanadium-containing compound may be any compound that is water-soluble and does not leave an anionic component as a residue upon heat crystallization. For example, ammonium vanadate, vanadium chloride, vanadium bromide, vanadium fluoride More preferably, ammonium vanadate is used.
ビスマスを含む化合物に添加する錯化剤としては、ビスマスイオンに配位でき、さらに好ましくは、ビスマスイオンに対して１当量で配位できるものが好適に用いられる。例えば、分子中に２つのカルボキシ基を有する水溶性カルボン酸等の親水性錯化剤を好ましく用いることができ、より好ましくは、水溶液中で、ビスマスイオンへの配位能が極めて高いエチレンジアミン四酢酸（ＥＤＴＡ）を用いることができる。 As the complexing agent added to the compound containing bismuth, those capable of coordinating to bismuth ions, and more preferably capable of coordinating with 1 equivalent to bismuth ions are preferably used. For example, a hydrophilic complexing agent such as a water-soluble carboxylic acid having two carboxy groups in the molecule can be preferably used, and more preferably ethylenediaminetetraacetic acid having an extremely high coordination ability to bismuth ions in an aqueous solution. (EDTA) can be used.
バナジウムを含む化合物に添加する錯化剤としては、バナジウムイオンに配位でき、さらに好ましくは、１当量で配位できるものが好適に用いられる。例えば、分子中に２つ以下のカルボキシ基、および１つ以上２つ以内の親水基を有する水溶性カルボン酸等の親水性錯化剤を好ましく用いることができ、より好ましくは、水溶液中で、バナジウムイオンへの配位能が極めて高い酒石酸を用いることができる。これにより、従来極めて水に難溶のビスマスイオンやバナジウムイオンを水溶化でき、さらに、親水部であるカルボキシ基が溶媒相側に露出した場合に起こる分子間での脱水重縮合による分子間重合を抑制できるため、熱分解時の結晶核の微細化が達成でき、熱分解反応後の粒子微細化が可能となる。 As the complexing agent added to the compound containing vanadium, those capable of coordinating with vanadium ions, and more preferably capable of coordinating with one equivalent are suitably used. For example, a hydrophilic complexing agent such as a water-soluble carboxylic acid having 2 or less carboxy groups in the molecule and 1 or more and 2 or less hydrophilic groups can be preferably used, and more preferably in an aqueous solution. Tartaric acid having extremely high coordination ability to vanadium ions can be used. As a result, bismuth ions and vanadium ions that have been extremely insoluble in water can be solubilized in the past, and intermolecular polymerization by dehydration polycondensation between molecules that occurs when the carboxy group, which is a hydrophilic part, is exposed to the solvent phase side. Since it can suppress, the refinement | miniaturization of the crystal nucleus at the time of thermal decomposition can be achieved, and the refinement | miniaturization of the particle | grains after a thermal decomposition reaction is attained.
本発明のＢｉＶＯ４粒子の製造において、水溶性バナジウム錯体を含む水溶液と水溶性ビスマス錯体を含む水溶液を混合して、ＢｉＶＯ４前駆体を含む水溶液を調製することが好ましい。これらの好ましい混合比率は、水１００重量部に対して、水溶性バナジウム錯体は、バナジウム換算で０．０００１〜０．０２モルであり、水溶性ビスマスを錯体は、ビスマス換算で０．０００１〜０．０２モルである。また、水溶性バナジウム錯体を形成するために添加する錯化剤は、バナジウム１モルに対して１〜１０倍モルであることが好ましい。また、水溶性ビスマス錯体を形成するために添加する錯化剤は、ビスマス１モルに対して１〜１０倍モルであることが好ましい。この比率で混合することで、ビスマスイオンおよびバナジウムイオンが良好に水溶化し、熱分解後の高結晶性化及び微細化が可能となる。この範囲以外では、加水分解反応の進行や、分子の疎水性向上による水溶性の低下が起こる恐れがある。また、ＢｉＶＯ４前駆体を含む水溶液のｐＨは、好ましくは２〜１０であり、より好ましくは、４〜１０である。この範囲とすることで、水溶液中での各イオンの安定性を維持し、結晶化後の微細化が可能になる。また、強酸・強アルカリ雰囲気による加水分解重縮合の促進による結晶粗大化を抑制できる。 In the production of BiVO 4 particles of the present invention, it is preferable to prepare an aqueous solution containing a BiVO 4 precursor by mixing an aqueous solution containing a water-soluble vanadium complex and an aqueous solution containing a water-soluble bismuth complex. These preferred mixing ratios are 0.0001 to 0.02 mol of the water-soluble vanadium complex in terms of vanadium with respect to 100 parts by weight of water, and the water-soluble bismuth complex is 0.0001 to 0 in terms of bismuth. 0.02 mole. Moreover, it is preferable that the complexing agent added in order to form a water-soluble vanadium complex is 1-10 times mole with respect to 1 mol of vanadium. Moreover, it is preferable that the complexing agent added in order to form a water-soluble bismuth complex is 1-10 times mole with respect to 1 mol of bismuth. By mixing at this ratio, the bismuth ions and vanadium ions are water-soluble satisfactorily, and high crystallinity and miniaturization after thermal decomposition are possible. Outside this range, the hydrolysis reaction may progress or the water solubility may decrease due to the improved hydrophobicity of the molecule. The pH of the aqueous solution containing the BiVO 4 precursor is preferably 2 to 10, and more preferably 4 to 10. By setting it as this range, the stability of each ion in aqueous solution is maintained, and refinement | miniaturization after crystallization is attained. Moreover, the crystal coarsening by acceleration | stimulation of the hydrolysis polycondensation by a strong acid and strong alkali atmosphere can be suppressed.
ＢｉＶＯ４前駆体を含む水溶液から、ＢｉＶＯ４粒子を製造する方法として、以下の方法が好ましく用いられる。ＢｉＶＯ４前駆体を含む水溶液を２００℃以下の低温で乾燥し、乾燥体を回収する。この乾燥体を結晶化する為に焼成することで、ＢｉＶＯ４粒子を製造することが可能である。また、この水溶液の乾燥および焼成工程を、連続的に行っても良い。ＢｉＶＯ４における結晶化の際の焼成温度は、４００℃を超え７００℃未満であり、より好ましくは、４５０℃以上６００℃以下である。この温度範囲とすることで、錯化剤の脱水重縮合により生成するポリマー粒子を熱分解しつつ、高純度なＢｉＶＯ４粒子を高度に結晶化することが可能となる。 As a method for producing BiVO 4 particles from an aqueous solution containing a BiVO 4 precursor, the following method is preferably used. The aqueous solution containing the BiVO 4 precursor is dried at a low temperature of 200 ° C. or lower, and the dried product is recovered. BiVO 4 particles can be produced by calcination to crystallize the dried body. Moreover, you may perform the drying and baking process of this aqueous solution continuously. The calcination temperature at the time of crystallization in BiVO 4 is more than 400 ° C. and less than 700 ° C., more preferably 450 ° C. or more and 600 ° C. or less. By adjusting to this temperature range, it is possible to highly crystallize high-purity BiVO 4 particles while thermally decomposing polymer particles generated by dehydration polycondensation of the complexing agent.
光触媒としての利用方法
本発明のＢｉＶＯ４粒子を光触媒として水の光分解に用いる場合、水素発生用光触媒とともに、水中に適当なレドックス対（Ｆｅ２＋／Ｆｅ３＋、［Ｃｏ（ｂｐｙ）３］３＋／２＋、［Ｃｏ（ｐｈｅｎ）３］３＋／２＋、Ｉ−／Ｉ３ −、Ｉ−／ＩＯ３ −、Ｃｏ２＋／Ｃｏ３+等）を溶解させるか、もしくは凝集や焼成などの手法により水素発生光触媒と接触させ、水を完全分解できるＺスキームシステムの構成とすることで、可視光照射により、水の完全分解が達成可能となる。本発明における水素発生用光触媒として、好ましくは、ロジウムドープチタン酸ストロンチウムである。
Method of Use as Photocatalyst When the BiVO 4 particles of the present invention are used as a photocatalyst for photolysis of water, a suitable redox couple (Fe 2+ / Fe 3+ , [Co (bpy) 3 ] 3 + / 2+ , [Co (phen) 3 ] 3 + / 2 + , I − / I 3 − , I − / IO 3 − , Co 2+ / Co 3+, etc.) or hydrogen generation by a technique such as aggregation or firing By contacting with a photocatalyst to form a Z scheme system that can completely decompose water, complete decomposition of water can be achieved by irradiation with visible light. The photocatalyst for hydrogen generation in the present invention is preferably rhodium-doped strontium titanate.
以下の実施例によって本発明をさらに詳細に説明する。なお、本発明はこれらの実施例に限定されるものではない。 The following examples further illustrate the present invention. The present invention is not limited to these examples.
ＢｉＶＯ ４ 粒子の作製
（実施例１〜４）
２０ｍＬサンプル瓶に、水１０ｇと錯化剤であるＬ−（＋）酒石酸（和光純薬製）０．００１７ｍｏｌ（０．２５３６ｇ）を添加し、室温で撹拌しながら、メタバナジン酸アンモニウム（アルドリッチ製）０．００１７ｍｏｌ（０．２０ｇ）添加し、５０℃で１時間撹拌して水溶性バナジウム錯体を含む赤茶色透明な水溶液を作製した。また、２０ｍＬサンプル瓶に、水１０ｇに、親水性錯化剤であるエチレンジアミン四酢酸（和光純薬製）０．０１７ｍｏｌ（０．４９４ｇ）を添加し、２５％アンモニア水を１ｇ滴下して水に溶解させた後、室温で撹拌しながら、硝酸ビスマス五水和物（和光純薬製）０．００１７ｍｏｌ（０．８２ｇ）添加し、室温で１時間撹拌して水溶性ビスマス錯体を含む無色透明な水溶液を作製した。
次いで、上記で作製した水溶性ビスマス錯体を含む水溶液に、水溶性バナジウム錯体を含む水溶液を添加して、室温で３時間撹拌を行った。これにより、ＢｉＶＯ４前駆体を含む青色透明な水溶液を得た。この水溶液のｐＨは、およそ８であった。
以上のように作製した、ＢｉＶＯ４前駆体水溶液を、８０℃で１時間乾燥させた後、表１に示す焼成温度および焼成時間で焼成することで、高温結晶化させ、ＢｉＶＯ４粒子を作製した。作製条件および特性については、表１にまとめる。
Preparation of BiVO 4 particles (Examples 1 to 4)
To a 20 mL sample bottle, 10 g of water and 0.0017 mol (0.2536 g) of L-(+) tartaric acid (manufactured by Wako Pure Chemical Industries) as a complexing agent are added and stirred at room temperature, while ammonium metavanadate (manufactured by Aldrich) 0.0017 mol (0.20 g) was added and stirred at 50 ° C. for 1 hour to prepare a red-brown transparent aqueous solution containing a water-soluble vanadium complex. Further, 0.017 mol (0.494 g) of ethylenediaminetetraacetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), a hydrophilic complexing agent, was added to 10 g of water in a 20 mL sample bottle, and 1 g of 25% ammonia water was added dropwise to the water. After dissolving, 0.0017 mol (0.82 g) of bismuth nitrate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring at room temperature, and the mixture was stirred at room temperature for 1 hour to be colorless and transparent containing a water-soluble bismuth complex. An aqueous solution was prepared.
Next, an aqueous solution containing a water-soluble vanadium complex was added to the aqueous solution containing the water-soluble bismuth complex prepared above, and the mixture was stirred at room temperature for 3 hours. As a result, a blue transparent aqueous solution containing the BiVO 4 precursor was obtained. The pH of this aqueous solution was approximately 8.
The BiVO 4 precursor aqueous solution prepared as described above was dried at 80 ° C. for 1 hour, and then fired at the firing temperature and firing time shown in Table 1 to be crystallized at a high temperature to produce BiVO 4 particles. . The manufacturing conditions and characteristics are summarized in Table 1.
（実施例５）
錯化剤として乳酸を用いた以外は、実施例１のＢｉＶＯ４粒子の作製方法と同様の方法にて、ＢｉＶＯ４粒子を作製した。
(Example 5)
Except for using lactic acid as complexing agent, in the same manner as the method for preparing the BiVO 4 particles of Example 1 were produced BiVO 4 particles.
（比較例１）
比較例１として、従来の固相反応法により作製したＢｉＶＯ４を作製した。固相反応法による作製方法は、以下の通りである。
酸化ビスマス（和光純薬製）、五酸化バナジウム（和光純薬製）の各粉末を、Ｂｉ：Ｖ＝１：１のモル比率となるように混合し、７００℃で８時間焼成し、比較例１のＢｉＶＯ４粉末を作製した。作製条件および特性については、表１にまとめる。
(Comparative Example 1)
As Comparative Example 1, BiVO 4 produced by a conventional solid phase reaction method was produced. The production method by the solid phase reaction method is as follows.
Each powder of bismuth oxide (manufactured by Wako Pure Chemical Industries) and vanadium pentoxide (manufactured by Wako Pure Chemical Industries) was mixed so as to have a molar ratio of Bi: V = 1: 1 and baked at 700 ° C. for 8 hours. 1 BiVO 4 powder was prepared. The manufacturing conditions and characteristics are summarized in Table 1.
（比較例２）
焼成温度を７００℃とした以外は、実施例１のＢｉＶＯ４粒子の作製方法と同様の方法にて、ＢｉＶＯ４粒子を作製した。作製条件および特性については、表１にまとめる。
(Comparative Example 2)
Except that the firing temperature was 700 ° C., at the same method as the method for manufacturing a BiVO 4 particles of Example 1 were produced BiVO 4 particles. The manufacturing conditions and characteristics are summarized in Table 1.
（比較例３）
焼成温度を４００℃とした以外は、実施例１のＢｉＶＯ４粒子の作製方法と同様の方法にて、ＢｉＶＯ４粒子を作製した。作製条件および特性については、表１にまとめる。
(Comparative Example 3)
Except that the firing temperature was 400 ° C., at the same method as the method for manufacturing a BiVO 4 particles of Example 1 were produced BiVO 4 particles. The manufacturing conditions and characteristics are summarized in Table 1.
ＢｉＶＯ ４ 粒子の結晶構造と微細構造
実施例および比較例で作製したＢｉＶＯ４のＸ線回折測定を行った。その結果、すべてのＢｉＶＯ４粒子が、単相のモノクリニック−シーライト構造を有することが明らかとなった。次いで、走査型電子顕微鏡による観察からＢｉＶＯ４粒子の一次粒子径を算出した。実施例の一例として、図３に５００℃で２時間焼成した後の粉末のＳＥＭ像を示す。一次粒子径は、１００ｎｍ以下であり、高温結晶化処理後も、微細な粒子形状を維持することが分かる。
X-ray diffraction measurement was performed on BiVO 4 produced in the examples and comparative examples of the crystal structure and microstructure of BiVO 4 particles . As a result, it was revealed that all BiVO 4 particles have a single-phase monoclinic-celite structure. It was then calculated primary particle diameter of BiVO 4 particles observed with a scanning electron microscope. As an example of the example, FIG. 3 shows an SEM image of the powder after baking at 500 ° C. for 2 hours. It can be seen that the primary particle diameter is 100 nm or less, and the fine particle shape is maintained even after the high temperature crystallization treatment.
ＢｉＶＯ ４ 粒子のＸ線構造解析によるピーク特性
実施例および比較例で作製したＢｉＶＯ４のＸ線構造回折スペクトルを以下の方法にて測定した。具体的には、Ｘ線回折装置（ＰＡＮａｌｙｔｉｃａｌ製）を用いて、Ｘ線管の運転条件が、２５℃の温度条件で、印加電圧４５ｋＶ、電流２００ｍＡであり、ブラッグ角２θ＝１０°〜６０°の範囲を、２θのスキャン速度が毎分２．５°で、０．０５°間隔で測定した。得られたＸ線強度から下記の式を用いて、Ｘ線強度比ＡおよびＸ線強度比Ｂを求めた。
Ｘ線強度比Ａ＝Ｉ（２θ＝１８．８°）／Ｉ（２θ＝１９．０°）
Ｘ線強度比Ｂ＝Ｉ（２θ＝３４．８５°）／Ｉ（２θ＝３４．５°）
Peak characteristics by X-ray structure analysis of BiVO 4 particles X-ray structure diffraction spectra of BiVO 4 prepared in Examples and Comparative Examples were measured by the following method. Specifically, using an X-ray diffractometer (manufactured by PANalytical), the operating conditions of the X-ray tube are a temperature condition of 25 ° C., an applied voltage of 45 kV, a current of 200 mA, and a Bragg angle 2θ = 10 ° to 60 °. Was measured at 0.05 ° intervals with a 2θ scan rate of 2.5 ° per minute. The X-ray intensity ratio A and the X-ray intensity ratio B were determined from the obtained X-ray intensity using the following formula.
X-ray intensity ratio A = I (2θ = 18.8 °) / I (2θ = 19.0 °)
X-ray intensity ratio B = I (2θ = 34.85 °) / I (2θ = 34.5 °)
ＢｉＶＯ ４ 粒子の水分解による酸素発生活性
実施例および比較例で作製したＢｉＶＯ４粒子の可視光照射による水分解活性を以下のような方法で調べた。パイレックス（登録商標）製上方照射用の窓付きのガラスフラスコに、ＢｉＶＯ４粉末０．２ｇと、犠牲試薬となる硝酸銀（和光純薬製）を２０ｍｍｏｌ／Ｌ含む水溶液１５０ｍｌを入れて、スターラーで撹拌しながら、反応溶液とした。そして、この反応溶液を入れたガラスフラスコを閉鎖循環装置（幕張理化学製）に装着し、反応系内の雰囲気をアルゴン置換した。そして、ＵＶカットフィルター（Ｌ−４２、ＨＯＹＡ製）を装着した３００Ｗキセノンランプ（Ｃｅｒｍａｘ製、ＰＥ−３００ＢＦ）により、可視光をパイレックス（登録商標）窓側から照射した。そして、光照射した後３時間の、水が酸化されて生成する酸素の発生量を、ガスクロマトグラフ（ＧＬサイエンス製、ＧＣ−８Ａ、ＴＣＤ検出器、ＭＳ−５Ａカラム）により経時的に調べた。
BiVO 4 Water degradation activity by irradiation of visible light BiVO 4 particles produced by oxygen evolution activity Examples and Comparative Examples with water decomposition of the particles were examined by the following method. In a glass flask with a window for upward irradiation made of Pyrex (registered trademark), 0.2 g of BiVO 4 powder and 150 ml of an aqueous solution containing 20 mmol / L of silver nitrate (manufactured by Wako Pure Chemical Industries) as a sacrificial reagent are added and stirred with a stirrer. The reaction solution was made. The glass flask containing the reaction solution was attached to a closed circulation device (Makuhari Chemical), and the atmosphere in the reaction system was replaced with argon. And visible light was irradiated from the Pyrex (registered trademark) window side by a 300 W xenon lamp (manufactured by Cermax, PE-300BF) equipped with a UV cut filter (L-42, manufactured by HOYA). Then, the amount of oxygen generated by oxidizing water for 3 hours after the light irradiation was examined over time by a gas chromatograph (manufactured by GL Science, GC-8A, TCD detector, MS-5A column).
Claims (5)
Ａ＝Ｉ（２θ＝１８．８°）／Ｉ（２θ＝１９．０°）≦０．８３
を満たすことを特徴とする、ＢｉＶＯ４粒子。 The primary particle size is 100 nm or less, the crystal structure measured by X-ray structural analysis is a monoclinic-celite structure, and the peak at the Bragg angle 2θ = 18.7 ° on the (101) plane is (011) The X-ray intensity I (2θ = 18.8 °) of the Bragg angle 2θ = 18.8 °, which is intermediate between the peak of the Bragg angle 2θ = 19.0 ° in the plane, is the Bragg angle 2θ = 19.19 in the (011) plane. The X-ray intensity ratio A obtained by dividing by 0 ° X-ray intensity I (2θ = 19.0 °) is expressed by the following formula:
A = I (2θ = 18.8 °) / I (2θ = 19.0 °) ≦ 0.83
BiVO 4 particles characterized by satisfying:
ビスマス化合物、バナジウム化合物及び錯化剤を水に溶解させた水溶液を、乾燥および焼成することを特徴とする、ＢｉＶＯ４粒子の製造方法。 A BiVO 4 of the manufacturing method according to any one of claims 1 to 3,
A method for producing BiVO 4 particles, comprising drying and firing an aqueous solution in which a bismuth compound, a vanadium compound and a complexing agent are dissolved in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013129216A JP5892478B2 (en) | 2013-06-20 | 2013-06-20 | BiVO4 particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013129216A JP5892478B2 (en) | 2013-06-20 | 2013-06-20 | BiVO4 particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015003840A true JP2015003840A (en) | 2015-01-08 |
| JP5892478B2 JP5892478B2 (en) | 2016-03-23 |
Family
ID=52300044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013129216A Active JP5892478B2 (en) | 2013-06-20 | 2013-06-20 | BiVO4 particles and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5892478B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017100057A (en) * | 2015-11-30 | 2017-06-08 | 国立研究開発法人産業技術総合研究所 | Semiconductor photocatalyst having characteristic absorption band and manufacturing method therefor |
| CN107827154A (en) * | 2017-12-08 | 2018-03-23 | 吉林师范大学 | The preparation method of sword-shaped monoclinic phase pucherite in a kind of hand of preferential exposure (040) crystal face |
| JP2019084527A (en) * | 2017-11-01 | 2019-06-06 | 株式会社豊田中央研究所 | Z scheme-type photocatalyst system |
| JP2020021658A (en) * | 2018-08-01 | 2020-02-06 | 国立研究開発法人産業技術総合研究所 | Battery system |
| CN116889875A (en) * | 2023-07-28 | 2023-10-17 | 中国科学院地理科学与资源研究所 | BiVO (binary organic acid) 4 CoAlLa-LDH composite photocatalyst, and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108636419A (en) * | 2018-03-14 | 2018-10-12 | 西安建筑科技大学 | A kind of pucherite-magnesium ferrite composite photo-catalyst, preparation method and applications |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3843554A (en) * | 1970-09-24 | 1974-10-22 | Du Pont | Catalyst compositions of scheelite crystal structure containing vanadium,bismuth and cation vacancies |
| 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 |
| JP2005035853A (en) * | 2003-07-18 | 2005-02-10 | Sk Kaken Co Ltd | Method of manufacturing bismuth vanadate particulate |
| JP2011178638A (en) * | 2010-03-03 | 2011-09-15 | Osaka Univ | Bismuth vanadate pigment |
| WO2012008838A1 (en) * | 2010-07-16 | 2012-01-19 | Universiteit Twente | Photocatalytic water splitting |
-
2013
- 2013-06-20 JP JP2013129216A patent/JP5892478B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3843554A (en) * | 1970-09-24 | 1974-10-22 | Du Pont | Catalyst compositions of scheelite crystal structure containing vanadium,bismuth and cation vacancies |
| 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 |
| JP2005035853A (en) * | 2003-07-18 | 2005-02-10 | Sk Kaken Co Ltd | Method of manufacturing bismuth vanadate particulate |
| JP2011178638A (en) * | 2010-03-03 | 2011-09-15 | Osaka Univ | Bismuth vanadate pigment |
| WO2012008838A1 (en) * | 2010-07-16 | 2012-01-19 | Universiteit Twente | Photocatalytic water splitting |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017100057A (en) * | 2015-11-30 | 2017-06-08 | 国立研究開発法人産業技術総合研究所 | Semiconductor photocatalyst having characteristic absorption band and manufacturing method therefor |
| JP2019084527A (en) * | 2017-11-01 | 2019-06-06 | 株式会社豊田中央研究所 | Z scheme-type photocatalyst system |
| CN107827154A (en) * | 2017-12-08 | 2018-03-23 | 吉林师范大学 | The preparation method of sword-shaped monoclinic phase pucherite in a kind of hand of preferential exposure (040) crystal face |
| JP2020021658A (en) * | 2018-08-01 | 2020-02-06 | 国立研究開発法人産業技術総合研究所 | Battery system |
| JP7109069B2 (en) | 2018-08-01 | 2022-07-29 | 国立研究開発法人産業技術総合研究所 | battery system |
| CN116889875A (en) * | 2023-07-28 | 2023-10-17 | 中国科学院地理科学与资源研究所 | BiVO (binary organic acid) 4 CoAlLa-LDH composite photocatalyst, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5892478B2 (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5892478B2 (en) | BiVO4 particles and method for producing the same | |
| Jalalah et al. | Comparative study on photocatalytic performances of crystalline α-and β-Bi2O3 nanoparticles under visible light | |
| Ravidhas et al. | Facile synthesis of nanostructured monoclinic bismuth vanadate by a co-precipitation method: Structural, optical and photocatalytic properties | |
| EP2459485B1 (en) | Photocatalytic materials and process for producing the same | |
| US9561493B2 (en) | Synthesis of pyrochlore nanostructures and uses thereof | |
| Wu et al. | Synthesis, structures and photocatalytic activities of microcrystalline ABi2Nb2O9 (A= Sr, Ba) powders | |
| Padmini et al. | Mesoporous rutile TiO2: Synthesis, characterization and photocatalytic performance studies | |
| JPWO2013180307A1 (en) | Visible light responsive photocatalyst particles and method for producing the same | |
| JP3845720B2 (en) | Potassium niobate photocatalyst and method for producing the same | |
| Fu et al. | Effect of calcination temperature on microstructure and photocatalytic activity of BiOX (X= Cl, Br) | |
| RU2549421C2 (en) | Method of obtaining nanoneedles of sodium vanadium oxide bronze | |
| Pan et al. | Zinc titanium glycolate acetate hydrate and its transformation to zinc titanate microrods: synthesis, characterization and photocatalytic properties | |
| Guru et al. | Influence of nature of surfactant and precursor salt anion on the microwave assisted synthesis of barium carbonate nanoparticles | |
| Goswami et al. | A novel synthetic approach for the preparation of sulfated titania with enhanced photocatalytic activity | |
| Obregón et al. | Water splitting performance of Er3+-doped YVO4 prepared from a layered K3V5O14 precursor | |
| JP6521316B2 (en) | Semiconductor photocatalyst having characteristic absorption band and method of manufacturing the same | |
| KR20140092483A (en) | Conversion method of crystal shape to control titanium dioxide | |
| JP4051433B2 (en) | Zinc oxide polycrystalline tube | |
| Zhang et al. | Photocatalytic activities of europium (III) and niobium (V) co-doped TiO2 nanopowders synthesized in Ar/O2 radio-frequency thermal plasmas | |
| RU2739773C1 (en) | Method of producing nanostructured hollow microspheres of vanadium oxide (versions) | |
| JP2008179528A (en) | Manufacture method of titanium oxide | |
| Hongsong et al. | Preparation, characterization of A2Ce2O7 (A= La and Gd) and their photo-catalytic properties | |
| Dogu et al. | Photocatalytic properties and characterization of praseodymium-doped titanium dioxide | |
| JP6218116B2 (en) | Composite metal oxide particles and method for producing the same | |
| JP2015020936A (en) | Method for producing tantalum-oxide nanowire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150410 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160122 |
|
| 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: 20160201 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5892478 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160214 |