Effects of zirconium (Zr) doping into BiVO4 electrode on its structural properties and photoelectrochemical (PEC) property for water oxidation were examined. The BiVO4 electrodes with different Zr contents were prepared via a spin-coating process. Structural analyses using XRD and Raman spectroscopy indicated that all the samples consisted of mixtures of monoclinic scheelite (ms-BiVO4) and tetragonal scheelite (ts-BiVO4) structures. The highest PEC property for water oxidation was achieved when the sample doped with a relatively small amount of Zr (i.e., 0.5% of Zr-doped BiVO4); further doping caused a reduction of PEC property, probably due to the enhancement of carrier recombination induced by such excess Zr components

Islam MD.Monirul

MD. Monirul Islam

Shigeru Ikeda

Shuji Nakanishi

Takashi Harada

Takato Kawaguchi

Takeaki Sakurai

中西 周次

原田 隆史

後藤 彩子

櫻井 岳暁

池田 茂

川口 誉人

Islam MD. Monirul

Takato KAWAGUCHI

Takashi HARADA

Syuji NAKANISHI

Takeaki SAKURAI

Shigeru IKEDA

Konan University Repository

KONAN UNIVERSITY水の光電気化学的酸化分解に活性な BiVO4薄膜光電極への Zr 添加効果著者 後藤 彩子, 原田 隆史, 中西 周次, IslamMD.Monirul, 櫻井 岳暁, 池田 茂雑誌名 甲南大学紀要. 理工学編巻 65号 1ページ 11-16発行年 2019-01-22URL http://doi.org/10.14990/00003209Ỉࡢග㟁Ẽ໬Ꮫⓗ㓟໬ศゎ࡟άᛶ࡞ BiVO4ⷧ⭷ග㟁ᴟ࡬ࡢ Zrῧຍຠᯝ ᕝཱྀ㄃ே 1㸪ཎ⏣㝯ྐ 2㸪୰す࿘ḟ 2㸪MD. Monirul Islam3㸪Ḉ஭ᓅᬡ 3㸪ụ⏣ ⱱ 1 1⏥༡኱Ꮫ⮬↛⛉Ꮫ◊✲⛉໬Ꮫᑓᨷ/⌮ᕤᏛ㒊ᶵ⬟ศᏊ໬Ꮫ⛉ 2኱㜰኱Ꮫኴ㝧࢚ࢿࣝࢠ࣮໬Ꮫ◊✲ࢭࣥࢱ࣮ 3⟃Ἴ኱Ꮫᩘ⌮≀㉁⣔≀⌮ᕤᏛᇦ㸦9᭶ 21᪥ཷ⌮, 9᭶ 28᪥᥇ᢥ㸧 ࠙せ᪨ࠚỈࡢග㟁Ẽ໬Ꮫⓗ㓟໬ศゎ࡟άᛶ࡞ BiVO4 ⷧ⭷ග㟁ᴟࡢ㧗ᶵ⬟໬ࢆ┠ⓗ࡜ࡋ࡚ࠊZr ࡢῧຍຠᯝࢆ᳨ウࡋࡓࠋࡇࡇ࡛ࡣࠊ᭷ᶵ⁐๣࡟⁐ゎࡍࡿྛ✀㔠ᒓ໬ྜ≀ཎᩱࢆ⏝࠸ࡓࢫࣆࣥࢥ࣮ࢺἲ࡟ࡼࡗ࡚ Zr ῧຍ㔞ࡢ␗࡞ࡿ BiVO4ⷧ⭷ࢆᡂ⭷ࡋࡓࠋXRD ࠾ࡼࡧ࣐ࣛࣥศග࡟ࡼࡿศᯒ࠿ࡽࠊᚓࡽࢀࡓ BiVO4ⷧ⭷ࡣ࠸ࡎࢀࡶࠊ༢ᩳᬗ⣔ࢩ࣮ࣛ࢖ࢺᵓ㐀㸦MS㸧࠾ࡼࡧṇ᪉ᬗ⣔ࢩ࣮ࣛ࢖ࢺᵓ㐀㸦TS㸧ࡀΰᅾࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ㓟⣲Ⓨ⏕࡟࠾ࡅࡿග㟁ᴟ≉ᛶࡣࠊZrῧຍ㔞ࡀẚ㍑ⓗᑡ࡞࠸ 0.5%Zrῧຍ BiVO4ⷧ⭷࡟࠾࠸࡚᭱ࡶⰋዲ࡞≉ᛶࡀᚓࡽࢀࡓࠋ࠙⥴ゝ ㏆ࠚᖺࠊ໬▼⇞ᩱ࡟௦ࢃࡿ࢚ࢿࣝࢠ࣮࡜ࡋ࡚ᮇᚅࡉࢀ࡚࠸ࡿỈ⣲ࡢࢡ࣮ࣜࣥ࡞〇㐀᪉ἲ࡜ࡋ࡚ࠊኴ㝧࢚ࢿࣝࢠ࣮ࢆ฼⏝ࡋࡓỈศゎࡀὀ┠ࡉࢀ࡚࠸ࡿࠋࡑࡢ᪉ἲࡢ୍ࡘ࡛࠶ࡿࠊỈ⣲Ⓨ⏕࡜㓟⣲Ⓨ⏕ࢆ஧✀㢮ࡢ༙ᑟయࢆ౑ࡗ࡚⾜࠺ Z ࢫ࣮࣒࢟ᆺࡢỈศゎ཯ᛂࡣࠊ㧗࠸ኴ㝧࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ㐩ᡂࡋᚓࡿࡇ࡜ࡀ⌮ㄽⓗ࡟ண ࡉࢀ࡚࠾ࡾ[1]ࠊ┒ࢇ࡟◊✲ࡉࢀ࡚࠸ࡿࠋZࢫ࣮࣒࢟ᆺࡢỈศゎ཯ᛂ࡟ࡣࠊ⢊ᮎࡢගゐ፹ࢆ⏝࠸ࡿ⣔࡜ග㟁ᴟࢆ⏝࠸ࡓග㟁Ẽ໬Ꮫ⣔ࡀ࠶ࡾࠊࡑࢀࡒࢀࡢ฼Ⅼࢆά࠿ࡋࡓపࢥࢫࢺ࡛㧗ᶵ⬟༙ᑟయᮦᩱࡸ཯ᛂࢩࢫࢸ࣒ࡀᥦ᱌ࡉࢀ࡚࠸ࡿࠋࢃࢀࢃࢀࡣࠊᚋ⪅ࡢග㟁Ẽ໬Ꮫ⣔࡟ὀ┠ࡋࠊpᆺ࢝ࣝࢥࢤࢼ࢖ࢻ༙ᑟయ࡛࠶ࡿCu2ZnSnS4໬ྜ≀ⷧ⭷ࢆỈ⣲Ⓨ⏕ࡢග㟁ᴟ㸦ග࢝ࢯ࣮ࢻ㸧ࠊnᆺ」ྜ㓟໬≀༙ᑟయ࡛࠶ࡿࣂࢼࢪࣥ㓟ࣅࢫ࣐ࢫ㸦BiVO4㸧ࢆ㓟⣲Ⓨ⏕ࡢග㟁ᴟ㸦ග࢔ࣀ࣮ࢻ㸧࡜ࡍࡿ཯ᛂ⣔࡟ࡘ࠸࡚ࠊࡑࢀࡒࢀࡢග㟁ᴟࡢ㧗ᶵ⬟໬࡟㛵ࡍࡿ◊✲ࢆ㐍ࡵ࡚࠸ࡿ[2]ࠋ  BiVO4ࡣྍどග㡿ᇦࡢᗈ࠸⠊ᅖࡢගࢆ྾཰ྍ⬟࡞ࣂࣥࢻࢠࣕࢵࣉ㸦Eg = 2.4㹼2.6 eV㸧ࢆ᭷ࡋࠊ౯㟁Ꮚᖏ࡟⏕ᡂࡍࡿṇᏍࡢ㓟໬ຊࡀ㧗࠸ࠊ᭷ᮃ࡞ග࢔ࣀ࣮ࢻࡢ୍ࡘ࡛࠶ࡿࠋBiVO4ࢆග࢔ࣀ࣮ࢻ࡟⏝࠸ࡿ◊✲ࡣࡍ࡛࡟ᗈࡃ⾜ࢃࢀ࡚࠾ࡾࠊBiVO4࡜ᑟ㟁ᛶᇶᯈࡢ㛫࡟ WO3ࢆᣳࡴࡇ࡜࡛᥋ゐ᢬ᢠࢆ㍍ῶ࡛ࡁࡿࡇ࡜[3]ࡸࠊBiVO4⾲㠃࡟ NiOOH/FeOOH ࢆ㓟⣲Ⓨ⏕ࡢゐ፹ࢧ࢖ࢺ࡜ࡋ࡚ᑟධࡍࡿࡇ࡜࡛ࠊ㓟⣲Ⓨ⏕࡟࠿࠿ࡿ㐣㟁ᅽࡀపῶ࡛ࡁࡿࡇ࡜[4]࡞࡝ࠊ㧗ᶵ⬟໬࡟㛵ࡍࡿሗ࿌ࡀࡉࢀ࡚࠸ࡿࠋBiVO4ࡣ⢊ᮎࡢ㓟⣲Ⓨ⏕ගゐ፹࡜ࡋ࡚ࡶάᛶ࡛࠶ࡾࠊZࢫ࣮࣒࢟ᆺࡢỈศゎ཯ᛂࡢ㓟⣲Ⓨ⏕ගゐ፹࡜ࡋ࡚ᗈࡃ᳨ウࡉࢀ࡚ࡁࡓࠋBiVO4ගゐ፹ࡢ㧗ᶵ⬟໬࡟࠾࠸࡚ࡣୖࠊ グࡢග㟁ᴟ࡛ࡶ⏝࠸ࡽࢀ࡚࠸ࡿゐ፹ࢧ࢖ࢺࡢᑟධ[5]ࡢ࡯࠿ࠊMoࡸ W࡞࡝ࡢ 6 ᪘ඖ⣲ࡢῧຍຠᯝࡀ▱ࡽ11Mem. Konan Univ., Sci. & Eng. Ser., 65 (1) 11～16 (2018)ࢀ࡚࠸ࡿ[6]ࠋࢃࢀࢃࢀࡣ᭱㏆ࠊ4᪘ඖ⣲࡛࠶ࡿࢪࣝࢥࢽ࣒࢘㸦Zr㸧ࡸࣁࣇࢽ࣒࢘㸦Hf㸧ࢆῧຍࡍࡿࡇ࡜࡛ࠊගゐ፹㓟⣲Ⓨ⏕཯ᛂࡢάᛶࡀྥୖࡍࡿࡇ࡜ࢆぢฟࡋࡓ[7]ࠋᮏ◊✲࡛ࡣࠊࡇࡢ4᪘ඖ⣲ࡢῧຍຠᯝࡢ୰࡛ࡶ Zr࡟ὀ┠ࡋࠊῧຍຠᯝࢆග㟁ᴟ⣔࡟㐺⏝ࡍࡿࡇ࡜࡛ࠊBiVO4ග࢔ࣀ࣮ࢻࡢ㓟⣲Ⓨ⏕࡟࠾ࡅࡿࡉࡽ࡞ࡿ㧗ᶵ⬟໬ࢆᐇ⌧ࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋ࠙ᐇ㦂ࠚ᪤ሗ[2]࡟ᚑࡗ࡚ࠊࣇࢵ⣲ࢻ࣮ࣉ㓟໬ࢫࢬ㸦FTO㸧ᑟ㟁⭷ࢆࢥ࣮ࢺࡋࡓ࢞ࣛࢫᇶᯈ㸦FTO/glass㸧ୖ࡟ࠊWO3ᒙ㸦⣙ 100 nm㸧࡜ BiVO4ᒙ㸦⣙ 80 nm㸧ࢆ✚ᒙࡉࡏࡓ BiVO4ග࢔ࣀ࣮ࢻࢆస〇ࡋࡓࠋ⾲㠃ࢆὙίࡋࡓ FTO/glass ࡟ WCl6ࡢ DMF ⁐ᾮࢆࠊFTO ᇶᯈୖ࡟ࢫࣆࣥࢥ࣮ࢺࡋࠊ500 Υ࡛↝ᡂࡍࡿࡇ࡜࡛ WO3 ᒙࢆሁ✚ࡉࡏࡓ㸦WO3/FTO/glass㸧ࠋᚓࡽࢀࡓWO3/FTO/glassୖ࡟ Bi࠾ࡼࡧ Vࡢࢫࣆࣥࢥ࣮ࢺᮦᩱ㸦SYM-BI05࠾ࡼࡧ V-02, 㧗⣧ᗘ໬Ꮫ㸧࡜ቑ⢓๣࡛࠶ࡿ࢚ࢳࣝࢭ࣮ࣝࣟࢫࢆྵࡴ㓑㓟ࣈࢳࣝ⁐ᾮࢆࢫࣆࣥࢥ࣮ࢺࡋࠊ550 Υ࡛ 30ศ㛫↝ᡂࡍࡿࡇ࡜࡛ࠊBiVO4ⷧ⭷ࢆ✚ᒙࡉࡏࡓࠋࡲࡓࠊBiVO4ⷧ⭷ࡢᡂ⭷᫬࡟ Zr ࡢࢫࣆࣥࢥ࣮ࢺᮦᩱ㸦SYM-ZR04, 㧗⣧ᗘ໬Ꮫ㸧ࢆຍ࠼ࡿࡇ࡜࡛ࠊZrࢆῧຍࡋࡓ BiVO4ⷧ⭷ࢆᡂ⭷ࡋࡓࠋZr ῧຍ㔞ࡣࠊᡂ⭷᫬ࡢ Zr ࢫࣆࣥࢥ࣮ࢺᮦᩱࡢ㔞࡟ࡼࡗ࡚ 0.5ࠥ1.0%࡟ㄪᩚࡋࡓࠋX ⥺ᅇᢡ㸦XRD㸧ࠊ࣐ࣛࣥศගศᯒ࠾ࡼࡧ㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾-࢚ࢿࣝࢠ࣮ศᩓᆺX⥺ศᯒ㸦SEM-EDX㸧ࢆ⏝࠸࡚ᚓࡽࢀࡓྛ BiVO4 ⷧ⭷ࡢᵓ㐀ࢆホ౯ࡋࡓࠋ㓟⣲Ⓨ⏕࡟࠾ࡅࡿග㟁ᴟ≉ᛶࡣࠊ୕㟁ᴟᘧ㟁Ẽ໬Ꮫࢭࣝࢆ⏝࠸࡚⾜ࡗࡓࠋAg/AgClࢆཧ↷㟁ᴟࠊPtࢆᑐᴟࠊࣜࣥ㓟⦆⾪ᾮ㸦pH 6.86㸧ࢆ㟁ゎᾮ࡜ࡋ࡚⏝࠸ࠊᨃఝኴ㝧ග㸦AM1.5G㸧ࢆ㛫Ḟⓗ࡟↷ᑕࡋ࡞ࡀࡽ㟁఩ᤄᘬࡍࡿࡇ࡜࡛ࠊ㟁ὶ-㟁఩᭤⥺ࢆᚓࡓࠋ ࠙⤖ᯝ࡜⪃ᐹࠚᚓࡽࢀࡓ BiVO4 ⷧ⭷ࡢ XRDࣃࢱ࣮ࣥࢆᅗ㸯࡟♧ࡍࠋXRDࣃࢱ࣮ࣥࡣࠊࡍ࡭࡚ FTOࠊWO3 ࡜BiVO4࡟ᖐᒓࡉࢀࠊBi2O3ࡸ V2O5࡜࡞࡝ࡢ㸰ඖ㓟໬≀࡞࡝ࡢ୙⣧≀࡟⏤᮶ࡍࡿᅇᢡ⥺ࡣぢࡽࢀ࡞࠿ࡗࡓࠋBiVO4࡟ࡣ༢ᩳᬗ⣔ࢩ࣮ࣛ࢖ࢺ㸦MS㸧࡜ṇ᪉ᬗ⣔ࢩ࣮ࣛ࢖ࢺ㸦TS㸧ࠊṇ᪉ᬗ⣔ࢪࣝࢥࣥ㸦TZ㸧ࡢ㸱ࡘࡢ⤖ᬗᵓ㐀ࡀ࠶ࡾࠊ㓟⣲Ⓨ⏕ගゐ፹࡜ࡋ࡚ࡣ MSᵓ㐀ࡀ᭱ࡶάᛶࡀ㧗࠸࡜࠸ࢃࢀ࡚࠸ࡿ[8]ࠋTZ ࡣ࡯࠿ࡢᵓ㐀࡜኱ࡁࡃᅇᢡࣃࢱ࣮ࣥࡀ␗࡞ࡗ࡚࠾ࡾࠊࡇࡇ࡛ࡢ࠸ࡎࢀࡢヨᩱ࡟ࡶྵࡲࢀ࡚࠸࡞࠸ࡇ࡜ࡀ☜ㄆࡉࢀࡓ୍ࠋ ᪉ࠊMS࡜ TSࡢᅇᢡࣃࢱ࣮ࣥࡣ࡯ࡰ୍⮴ࡋ࡚࠸ࡿࡓࡵ༊ู࡛ࡁ࡞࠿ࡗࡓࠋࡑࡇ࡛ྛࠊ ⷧ⭷ࡢ࣐ࣛࣥࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓࠋ⤖ᯝࢆᅗ㸰࡟♧ࡍࠋ࠸ࡎࢀࡢヨᩱࡶ V-Oࡢᑐ⛠ఙ⦰᣺ື࡟ᖐᒓࡉࢀࡿᙉ࠸ࣆ࣮ࢡ㸦νs(V-O)㸧࡜ V-O ࡢ㠀ᑐ⛠ఙ⦰᣺ື࡟ᖐᒓࡉࢀࡿᙅ࠸ࣆ࣮ࢡ㸦νas(V-O)㸧ࡀほ ࡉࢀࡓࠋνs(V-O)࡟ὀ┠ࡍࡿ࡜ࠊᩥ⊩࠿ࡽࡣࠊMS ࡛ࡣࠊ830 cm-1ࠊTS࡛ࡣ 823 cm-1࡟ࡑࢀࡒࢀࣆ࣮ࢡࢺࢵࣉࡀ⌧ࢀࡿ࡜ண᝿ࡉࢀ࡚࠸ࡿ[9]ࠋ௒ᅇࡢヨᩱ࠿ࡽᅗ㸯 %L92ග㟁ᴟࡢ ;5' ࣃࢱ࣮ࣥ??　?? ? ??　?? ? ??　?? ? MD.Monirul Islam ? ??　?? ? ??　?12ᚓࡽࢀࡓࢫ࣌ࢡࢺࣝࡣ࠸ࡎࢀࡶ⥺ᖜࡀᗈࡃࠊ⥺ᖜࡢᗈࡀࡾࡣࠊࡑࢀࡽMS ࡜ TS ࡢ୧᪉࡟⏤᮶ࡍࡿࣆ࣮ࢡࡀ㔜࡞ࡾ࠶ࡗࡓࡓࡵ࡜⪃࠼ࡽࢀࡓࠋࡍ࡞ࢃࡕࠊ࠸ࡎࢀࡢヨᩱࡶࠊMS ࡜TS ୧ᵓ㐀ࡀΰᅾࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋᚓࡽࢀࡓⷧ⭷࡟ࡘ࠸࡚ࠊSEM-EDX ᐃࢆ⾜࡞ࡗࡓྛࠋ ヨᩱࡢ⾲㠃ࡢ SEM ീࢆᅗ㸱࡟♧ࡍࠋᓥ≧ࡢᵓ㐀ࡀほᐹࡉࢀࠊࡑࡢᙧ≧࡟ࡣヨᩱ㛫࡛ࡢ᭷ពᕪࡀぢࡽࢀ࡞࠿ࡗࡓࡇ࡜࠿ࡽࠊZrῧຍࡀሁ✚ࡉࢀࡓヨᩱࡢࣔࣝࣇ࢛ࣟࢪ࣮࡟ࡣᙳ㡪ࢆ୚࠼࡚࠸࡞࠸ࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡲࡓࠊEDXศᯒ࠿ࡽࠊᓥ≧ᵓ㐀㒊ศࡀ BiVO4࡛࠶ࡾࠊᾏ≧࡟ぢ࠼ࡿพ㒊࠿ࡽࡣࠊࢱࣥࢢࢫࢸࣥ㸦W㸧ࡀ᳨ฟࡉࢀࡓࡇ࡜࠿ࡽࠊBiVO4ࡢୗᒙࡢWO3ࡶ୍㒊㟢ฟࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡓࠋ࡞࠾ࠊᓥ≧ element / atom% sample Bi V Bi/V ratio BiVO4 49.6 50.4 0.98 0.5%Zr-BiVO4 49.6 50.4 0.98 0.7%Zr-BiVO4 49.8 50.2 0.99 1.0%Zr-BiVO4 49.7 50.3 0.99 ᅗ㸰 BiVO4ග㟁ᴟࡢ࣐ࣛࣥࢫ࣌ࢡࢺࣝ⾲㸯 BiVO4ග㟁ᴟࡢ EDX⤖ᯝᅗ㸱 BiVO4ග㟁ᴟࡢ⾲㠃 SEM?の??????????に??な BiVO4?????への Zr ???? 13ᵓ㐀㒊ศࡢ Bi࡜ Vࡢྵ᭷㔞ࢆᐃ㔞ࡍࡿ࡜ࠊ࠸ࡎࢀࡢヨᩱࡶ Bi࡜ Vࡀ BiVO4ࡢ໬Ꮫ㔞ㄽẚ㸦Bi/V = 1㸧࡟࡯ࡰ୍⮴ࡍࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓ㸦⾲㸯㸧ࠋࡲࡓࠊZr ῧຍヨᩱ࡟ࡘ࠸࡚ࡣࡑࡢྵ᭷㔞ࡀᑡ࡞࠸ࡓࡵ௒ᅇࡢ EDX ᐃ࡛ࡣ☜ㄆ࡛ࡁ࡞࠿ࡗࡓࠋ ᅗ㸲࡟௒ᅇᚓࡽࢀࡓⷧ⭷ࢆ⏝࠸ࡓ඾ᆺⓗ࡞㟁ὶ-㟁఩≉ᛶࢆ♧ࡍࠋ࠸ࡎࢀࡢヨᩱ࡟࠾࠸࡚ࡶ㟁఩ࢆṇഃ࡟ᤄᘬࡍࡿ࡟ࡘࢀ࡚㓟⣲Ⓨ⏕࡟ࡼࡿ࢔ࣀ࣮ࢻග㟁ὶࡀほᐹࡉࢀࡓࠋ᫂ࡽ࠿࡟ࠊZr ࢆ 0.5%ῧຍࡋࡓග㟁ᴟ㸦0.5%Zr-BiVO4㸧ࡀ Zr ↓ῧຍࡢ BiVO4 ග㟁ᴟ㸦BiVO4㸧ࡼࡾࡶ኱ࡁ࡞㟁ὶᐦᗘࢆ♧ࡋࠊ౛࠼ࡤࠊ኱ࡁࡃ࢔ࣀ࣮ࢻศᴟࡋࡓ 1.2 V㸦vs RHE㸧࡛ࡢ㟁ὶᐦᗘࡣ BiVO4 ග㟁ᴟࡀ 586 μA/cm2 ࡛࠶ࡗࡓࡢ࡟ᑐࡋࠊ0.5%Zr-BiVO4 ග㟁ᴟ࡛ࡣ 844 μA/cm2࡜࡞ࡗࡓࠋ୍᪉ࠊZr ῧຍ㔞ࡀࡉࡽ࡟ከ࠸ග㟁ᴟ࡛ࡣ㟁ὶᐦᗘࡀྠ⛬ᗘ࠿ᑠࡉࡃ࡞ࡗࡓ㸦0.7%Zr-BiVO4: 593 μA/cm2ࠊ1.0%Zr-BiVO4: 488 μA/cm2㸧ࠋࡲࡓࠊ࢜ࣥࢭࢵࢺ㡿ᇦ㸦0.6 V vs RHE㸧ࡢ㟁ὶᐦᗘࡶ 0.5%Zr-BiVO4࡛ẚ㍑ⓗ኱ࡁࡃ࡞ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ㸦BiVO4: 129 μA/cm2ࠊ0.5%Zr-BiVO4: 152 μA/cm2ࠊ0.7%Zr-BiVO4: 123 μA/cm2ࠊ1.0%Zr-BiVO4: 92 μA/cm2㸧ࠋ ィ⟬⛉Ꮫⓗ࡞᳨ウ࡟ࡼࢀࡤࠊZr ࡣ BiVO4୰ࡢ Biࢧ࢖ࢺ࡟⨨᥮ࡉࢀࡿ࡜࠸࠺ࡇ࡜ࡀண᝿ࡉࢀ࡚࠸ࡿ[10]ࠋZrࡣ Biࡼࡾࡶ౯㟁Ꮚࡀ୍ࡘከ࠸ࡓࡵࠊࡑࡢࡼ࠺࡞ࢧ࢖ࢺ⨨᥮ࡀ㉳ࡇࡿ࡜ࠊ㐣๫㟁ᏊࡀⓎ⏕ࡍࡿࠊࡍ࡞ࢃࡕ nᆺࢻ࣮ࣆࣥࢢ࡜࡞ࡿࠋࡋࡓࡀࡗ࡚ࠊᑡ㔞ࡢ Zrࡢῧຍࡣࠊ࢟ࣕࣜ࢔⃰ᗘࡢቑຍ࡟ࡼࡿ㟁Ⲵศ㞳ࡢಁ㐍㸦ࣂࣥࢻ࣋ࣥࢹ࢕ࣥࢢࡢ᭤⋡ࡢቑ኱➼㸧࡟㉳ᅉࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊZr ࡢῧຍ㔞ࡀከࡃ࡞ࡿ࡜ࠊ✵ஈᒙཌࡢῶᑡࡸࢻ࣮ࣃࣥࢺ࡟ࡼࡿ࢟ࣕࣜ࢔෌⤖ྜࡢಁ㐍࡟ࡼࡗ࡚㟁Ⲵศ㞳ຠ⋡ࡀపୗࡍࡿࡓࡵࠊ㓟⣲Ⓨ⏕㟁ὶ㸦ᐦᗘ㸧ࡀῶᑡࡋࡓ࡜᥎ᐹࡉࢀࡿࠋࡲࡓࠊῧຍࡋࡓ Zrࡢ୍㒊ࡀ Biࢧ࢖ࢺࢆ⨨᥮ࡏࡎࠊ୙⣧≀࡜ࡋ࡚⾲㠃ࡸ⤖ᬗ᱁Ꮚ୰ࡢ࡯࠿ࡢ఩⨨࡟ධࡿࡇ࡜࡛ࠊ෌⤖ྜ୰ᚰ࡜࡞ࡗࡓࡓࡵ࡛࠶ࡿ࡜ࡶ⪃࠼ࡿࡇ࡜ࡶ࡛ࡁࡿࠋ௒ᚋࠊῧຍࡋࡓ Zr࡟ࡘ࠸࡚ࡢ⾲㠃࠶ࡿ࠸ࡣࣂࣝࢡෆ࡛ࡢ≧ែศᯒࡸࠊZrࡢῧຍ࡟ࡼࡿ࢟ࣕࣜ࢔⃰ᗘࡢኚ໬࠾ࡼࡧගບ㉳࡟ࡼࡗ࡚⏕ᡂࡋࡓ࢟ࣕࣜ࢔ࡢᑑ࿨ ᐃ࡞࡝࡟ࡼࡾࠊZrῧຍ࡟ࡼࡿ≀ᛶ࡬ࡢᙳ㡪ࢆ᫂ࡽ࠿࡟ࡋ࡚࠸ࡃᚲせࡀ࠶ࡿࠋ࠙ㅰ㎡ࠚᮏ◊✲ࡣ᪥ᮏᏛ⾡᣺⯆఍⛉Ꮫ◊✲㈝᪂Ꮫ⾡㡿ᇦ◊✲㸦␒ྕ㸸JP18H05183㸧࠾ࡼࡧᇶ┙◊✲ C㸦␒ྕ㸸JP18K05010㸧ࡢຓᡂ࡛⾜ࢃࢀࡓࠋグࡋ࡚ឤㅰࡍࡿࠋ ᅗ㸲 BiVO4ග㟁ᴟࡢග㟁Ẽ໬Ꮫ ᐃ⤖ᯝ??　?? ? ??　?? ? ??　?? ? MD.Monirul Islam ? ??　?? ? ??　?14ཧ⪃ᩥ⊩[1] M. S. Prévot et al., J. Phys. Chem. C, 117, 17879 (2013)[2] F. Jiang et al., J. Am. Chem. Soc., 137, 13691 (2015)[3] K. Fuku et al., Chem.Commun, 52, 5406 (2016)[4] T. W. Kim et al., Science, 343, 990 (2014)[5] A. Iwase, et al., J. Am. Chem. Soc., 133, 11054 (2011)[6] S. Berglund et al., Phys. Chem. Chem. Phys., 14, 7065 (2012)[7] S. Ikeda et al., Front. Chem., 6, 266 (2018)[8] S. Nikam et al., RSC Adv., 6, 107463 (2016)[9] V. I. Merupo et al., Mater. Sci. Semicond. Proc., 31, 618 (2015)[10] W.-J. Yin et al., Phys. Rev. B, 83, 155102 (2011)?の??????????に??な BiVO4?????への Zr ???? 15Impacts of Zr-doping in BiVO4 thin-film electrode on its photoelectrochemical property for water oxidation Takato Kawaguchi1, Takashi Harada2, Shuji Nakanishi2, MD. Monirul Islam3, Takeaki Sakurai3, Shigeru Ikeda1 1Department of Chemistry, Konan University, Kobe, Hyogo 658-8501, Japan 2Research Center for Solar Energy Chemistry, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan  3Institute of Applied Physics, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan (Received September 21, 2018, Accepted September 28, 2018) Abstract: Effects of zirconium (Zr) doping into BiVO4 electrode on its structural properties and photoelectrochemical (PEC) property for water oxidation were examined. The BiVO4 electrodes with different Zr contents were prepared via a spin-coating process. Structural analyses using XRD and Raman spectroscopy indicated that all the samples consisted of mixtures of monoclinic scheelite (ms-BiVO4) and tetragonal scheelite (ts-BiVO4) structures. The highest PEC property for water oxidation was achieved when the sample doped with a relatively small amount of Zr (i.e., 0.5% of Zr-doped BiVO4); further doping caused a reduction of PEC property, probably due to the enhancement of carrier recombination induced by such excess Zr components. ??　?? ? ??　?? ? ??　?? ? MD.Monirul Islam ? ??　?? ? ??　?16

水の光電気化学的酸化分解に活性な BiVO4薄膜光電極への Zr 添加効果

https://konan-u.repo.nii.ac.jp/?action=repository_action_common_download&item_id=3235&item_no=1&attribute_id=22&file_no=1

水の光電気化学的酸化分解に活性な BiVO4薄膜光電極への Zr 添加効果

Abstract

Similar works

Full text

Available Versions

Konan University Repository