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Fabrication of Template-Assisted CoreShell- and Hollow-Structured Titania
Composites from MnCO3 Microspheres

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ർ਻ᎺᏒ┙ᄢቇᄢቇ㒮࿖㓙ⅣႺᎿቇ⎇ⓥ⑼ ᢎ᝼㩷Ꮏቇඳ჻ ᧘ ਒␭     5GWPI9QQ.GG㩷

ർ਻ᎺᏒ┙ᄢቇᄢቇ㒮࿖㓙ⅣႺᎿቇ⎇ⓥ⑼

᧘ ቇᩮ

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ࠦࠕ㨺ࠪࠚ࡞߹ߚߪਛⓨ᭴ㅧࠍ᦭ߔࠆᣂⷙ

᭴ㅧߩ TiO2 ߪ‫ޔ‬㜞Ყ⴫㕙Ⓧ‫ޔ‬ૐኒᐲ‫ޔ‬㜞ᶐㅘᕈߥ

MnCO3/TiO2 ⶄว૕ߩวᚑߦ MnCO3 ᓸ☸ሶࠍ↪޿ߚ‫ޕ‬

ߤߩ․ᓽ߆ࠄ‫⸅ޔ‬ᇦ 5)‫࡯ࠨࡦ࠮ޔ‬6)‫࡝࠺ࠣ࠶࡜࠼ޔ‬ੑߟߩ⇣ߥࠆᒻᘒߪ‫ޔ‬MnCO3 ᓸ☸ሶߩ[NH4]2TiF6 ߣࡃ࡝࡯ߩࠠࡖ࡝ࠕ 7)ߥߤ߳ߩᔕ↪߇ᦼᓙߐࠇߡ޿ࠆ‫ޕ‬ߩ੍஻෻ᔕߩ෻ᔕᤨ㑆ࠍ೙ᓮߔࠆߎߣߢน⢻ߢ޽ㅢᏱ‫ޔ‬ਛⓨ᭴ㅧߩ᧚ᢱߪ‫ࠍ࠻࡯࡟ࡊࡦ࠹ޔ‬೑↪ߔߞߚ‫ޔߚ߹ޕ‬600 °C ߢߩ὾⚿ᓟߦࠦࠕ㨺ࠪࠚ࡞ߣਛ

ࠆ㍌ဳᴺߣ࠹ࡦࡊ࡟࡯࠻ࠍ೑↪ߒߥ޿㕖㍌ဳᴺߩⓨ᭴ㅧߩ Mn2O3/TiO2 ⶄว૕ߦᄌൻߒߚ‫↢ޕ‬ᚑ‛ߩਔᣇ߆ࠄᓧࠄࠇࠆ‫ޕ‬㍌ဳᴺߪ‫࡯࡟ࡊࡦ࠹ߦ⊛⥸৻ޔ‬ಽᨆߦ X ✢࿁᛬‫⿛ޔ‬ᩏဳ㔚ሶ㗼ᓸ㏜‫ࠛ࡝࡯ࡈޔ‬ᄌ឵࠻ߩౣ⃻ᕈߦఝࠇ‫ߚ߹ޔ‬Ꮏ⒟߇◲නߢ޽ࠆߚ߼‫ޔ‬᭴⿒ᄖಽశᴺ‫ޔ‬ㅘㆊဳ㔚ሶ㗼ᓸ㏜ࠍ↪޿ߚ‫ޕ‬὾⚿ᓟߩㅧ೙ᓮ߇ኈᤃߢ޽ࠅ 5)‫ޔ‬ฎߊ߆ࠄࠟࠬࡃࡉ࡞ 8)‫ࠛޔ‬↢ᚑ‛ߩ‛ᕈ⹏ଔߩߚ߼ߦ‫ߩ࡯࡞ࡉࡦ࡟࠴ࡔޔ‬ๆ⌕ࡑ࡞࡚ࠫࡦ‫ ࡞࠮ࡒޔ‬9,10)ߥߤߩࠃ߁ߥ࠰ࡈ࠻ߥ࠹ࡦ

․ᕈࠍ⺞ߴߚ‫ࠕࠦޕ‬㨺ࠪࠚ࡞ߣਛⓨ᭴ㅧߩࡊ࡟࡯࠻ߣ‫☸ࠬࠢ࠶࠹࡜࡯ࡑ࡝ࡐޔ‬ሶ 11,12)‫ޔ‬නಽᢔ

Mn2O3/TiO2 ⶄว૕ߣ߽ࡔ࠴࡟ࡦࡉ࡞࡯ߦ㕖Ᏹߦ㜞

ࠪ࡝ࠞ 13,14)‫⁁⃿ࡦࡏ࡯ࠞޔ‬૕ 15)ߥߤߩࠃ߁ߥࡂ࡯࠼

޿ๆ⌕⢻ജࠍ␜ߒ‫ ߡ޿߅ߦࠇߙࠇߘޔ‬5.2 ߣ 6.4 molߥ࠹ࡦࡊ࡟࡯࠻߇૶↪ߐࠇߡ޿ࠆ‫ޕ‬὾⚿߹ߚߪࠛ࠶

g–1 ߩๆ⌕ኈ㊂߇ᓧࠄࠇߚ‫⎇ᧄޕ‬ⓥᚻᴺߪ‫ޔ‬᭽‫ߥޘ‬࠴ࡦࠣߦࠃࠅ↪޿ߚ࠹ࡦࡊ࡟࡯࠻ࠍ㒰෰ߔࠆߎߣ

㊄ዻ὇㉄Ⴎ߳ߩㆡ↪߇น⢻ߢ޽ࠅ‫ޔ‬ᄙ᭽ߥᒻᘒߣ‛ߢ⁛․ߥਛⓨ᭴ㅧࠍᓧࠆߎߣ߇ߢ߈ࠆ‫ࡐޔ߫߃଀ޕ‬ᕈࠍ᦭ߔࠆᣂⷙ㉄ൻ࠴࠲ࡦⶄว૕ߩ㐿⊒ߦᔅⷐߥ࡝ࡑ࡯☸ሶߩ࠹ࡦࡊ࡟࡯࠻਄ߦ੤੕Ⓧጀᴺߢဋ৻

ᣇᴺ⺰ࠍឭଏߔࠆ‫ޕ‬

ߥ TiO2 ⤑ࠍ૞⵾ߒ‫ࠍ࠻࡯࡟ࡊࡦ࠹ޔ‬㒰෰ߔࠆߎߣ
ߢࡑࠗࠢࡠࠞࡊ࠮࡞ߩࠃ߁ߥਛⓨ᭴ㅧߩ TiO2 ☸ሶ㧝㧚ߪߓ߼ߦ

ࠍวᚑߔࠆᣇᴺ߇ᐢ▸ߦ૶↪ߐࠇߡ޿ࠆ߇‫ߦ⤑⵾ޔ‬㉄ൻ࠴࠲ࡦ(એਅ‫ޔ‬TiO2)᧚ᢱߪ‫㉄ޔ‬ൻജ߇ᒝߊ‫ޔ‬ⅣႺ⽶⩄߿Ქᕈ߇ૐ޿‫ޔ‬శ⸅ᇦᵴᕈ߇㜞޿ߥߤߩ࡙

ᤨ㑆ߣᚻ㑆߇߆߆ࠆߚ߼‫ޔ‬ല₸⊛ߥᣇᴺߣߪ⸒޿ߦ
ߊ޿ 5,16)‫ޕ‬࠾࡯ࠢߥ․ᕈ߆ࠄ᏷ᐢ޿ಽ㊁ߦ߅޿ߡ㜞޿㑐ᔃࠍᧄ⎇ⓥߪ‫ޔ‬Deki17–19) ࠄߦࠃߞߡឭ᩺ߐࠇߚ TiO2

㓸߼ߡ޿ࠆ‫ߩߘߩߢ࡞ࡌ࡟ࡁ࠽ߪߚ߹ࡠࠢࠗࡑޕ‬ᒻ⭯⤑ߩ⵾ㅧᣇᴺߢ޽ࠆᶧ⋧ၸⓍᴺ㧔liquid phaseᘒ೙ᓮߪ‫ᦨޔ‬ㄭߩਥߥ⎇ⓥὶὐߦߥߞߡ޿ࠆ‫ࠇߎޕ‬deposition㧦એਅ‫ޔ‬LPD㧕ࠍᔕ↪ߒߡ‫ޔ‬὇㉄ࡑࡦࠟࡦ߹ߢࡢࠗࡗ ‫ࡓ࡞ࠖࡈޔ ࡉ࡯ࡘ࠴ޔ‬ߥߤࠍ฽߻㧔એਅ‫ޔ‬MnCO3㧕ᓸ☸ሶߣ TiO2 ࠍⶄวൻߔࠆߚ߼

᭽‫᧚ࡁ࠽ߥޘ‬ᢱ߇㐿⊒ߐࠇߡ߈ߚ‫ߩߘޕ‬ਛߢ߽ਛⓨߩᣂߒ޿ࠕࡊࡠ࡯࠴ࠍ⚫੺ߔࠆ‫ޕ‬೨㚟૕ߢ޽ࠆࡋࠠ

1)

11

2)

3,4)

フジコー技報−tsukuru No. ࠨࡈ࡞ࠝࡠ࠴࠲ࡦ㉄ࠕࡦࡕ࠾࠙ࡓ[(NH4)2TiF6]ߩ㒶㉄㧔H3BO3㧘Wako Pure Chemical Industries㧘Ltd.㧕ߪ‫ޔ‬ࠗࠝࡦ㍲૕ߢ޽ࠆ TiF62–ߪ‫ޔ‬Mn2+ߣߩ㕒㔚⋧੕૞↪

⾼౉ߒߡ♖⵾ߥߒߦߘߩ߹߹૶↪ߒߚ‫ޕ‬⣕ࠗࠝࡦ᳓ߦࠃߞߡ MnCO3 ᓸ☸ሶߦๆ⌕ߒ‫ޔ‬LPD ෻ᔕߣߣ߽

㧔 18.2 M cm-1 㧕 ߪ ‫ ࡦ ࠝ ࠗ ޔ‬੤ ឵ ߅ ࠃ ߮ ỹ ㆊߦࠦࠕ㨺ࠪࠚ࡞߹ߚߪਛⓨ᭴ㅧߩ MnCO3/TiO2 ⶄว(Millipore, Direct-QTM) ߦ⛯޿ߡㅒᶐㅘߦࠃࠅᓧߚ‫ޕ‬૕ߦᄌൻߔࠆ‫ޕ‬ᄙߊߩ⎇ⓥߦ߅޿ߡ‫ޔ‬TiO2 ߣ㉄ൻࡑࡦࠟࡦߣߩⶄ

 ⃿⁁ /P%1 ᓸ☸ሶߩวᚑ

วൻ߇⺖㗴ߣߒߡ᜼ߍࠄࠇߡ޿ࠆ‫ޔ߫߃଀ޕ‬Ḩᑼ฽නಽᢔߩ MnCO3 ᓸ☸ሶߪ‫ޔ‬Antipov37)ࠄߦࠃࠅႎ

ᶐᴺࠍ↪޿ߡᓧࠄࠇߚࡑࡦࠟࡦ㉄ൻ‛ࠍᜂᜬߒߚ

๔ߐࠇߚᴉᲚᴺࠍᔕ↪ߒߡวᚑߒߚ‫◲ޕ‬නߦㅀߴࠆ

TiO2 ߪ‫㉄⚛⓸ޔ‬ൻ‛ࠍㆬᛯ⊛ߦ⸅ᇦㆶరߔࠆߎߣ߇

ߣ‫ޔ‬0.14M ߩ NaHCO3 ᳓ṁᶧࠍ 0.014M ߩ MnSO4 ߩߢ߈ࠆ‫ ㉄ ޔ ߚ ߹ ޕ‬ൻ ࡑ ࡦ ࠟ ࡦ ࠍ ฽ ߻ TiO2

᳓́ࠛ࠲ࡁ࡯࡞㧔5㧑‫ޔ‬v/ v㧕ᷙวṁᇦߦᠣᜈߒߥ߇

㧔MnOx–TiO2㧕ⶄว૕ߪ‫᦭ޔ‬ᯏ‛⾰ߩ㉄ൻ෻ᔕࠍ⸅

ࠄᷝടߒߚ‫ޕ‬4 ᤨ㑆ᠣᜈ෻ᔕᓟ‫ޔ‬ᓧࠄࠇߚᴉᲚ‛ࠍᇦߔࠆࠈㆊߒ‫ࡦࠝࠗޔ‬੤឵᳓ߣࠛ࠲ࡁ࡯࡞ߢᵞᵺߒߚᓟ‫ޔ‬

20)

21)

ߛߌߢߥߊ᳓ṁᶧߦሽ࿷ߔࠆ᦭ᯏᳪᨴ‛ߩಽ⸃ߦ߽ലᨐ⊛ߢ޽ࠆߎߣ߇ႎ๔ߐࠇߡ޿ࠆ 22)‫ޕ‬⚿᥏ᕈࠍ߽ߟ TiO2 ߩ◲ଢߥวᚑᣇᴺߩ㐿⊒ߪ‫ޔ‬วᚑߦ߆߆ࠆࠦࠬ࠻ࠍૐᷫߐߖ‫ޔ‬TiO2 ߩᔕ↪▸࿐ࠍ60 ͠ߢੇ῎ߒ࿁෼ߒߚ‫ޕ‬ .2& ᴺߦࠃࠆ 6K1 ࠦ࡯࠹ࠖࡦࠣ

ࠃࠅᐢߍࠆߩߦᄢ߈ߥᗧ⟵߇޽ࠆ‫ޕ‬LPD ᴺߪ‫ޔ‬ၮᧄ

 50 PJߩMnCO3ᓸ☸ሶࠍ10 mLߩ[NH4]2TiF6᳓ṁ⊛ߦᰴߩࠃ߁ߥ෻ᔕߢ᭴ᚑߐࠇߡ޿ࠆ 23)‫ޔߕ߹ޕ‬᳓ᶧ㧔0.1 M㧕ߦᷝടߒ‫ޔ‬2ᤨ㑆߹ߚߪ6ᤨ㑆ࠁߞߊࠅߦࠃࠆ TiF6 ߩട᳓ಽ⸃෻ᔕ߇㐿ᆎߐࠇ‫ࠗ⚛࠶ࡈޔ‬ߣᡬᜈߐߖߥ߇ࠄ੍஻෻ᔕ㧔prereaction㧕ࠍⴕߞߚ‫ޕ‬ࠝࡦߩ᝝ᝒ೷ߣߒߡࡎ࠙㉄ࠍᷝടߔࠆߎߣߢ㧔෻ᔕ⛯޿ߡ‫ޔ‬10 mLߩH3BO3᳓ṁᶧ㧔0.2 M㧕ࠍട߃‫ߐޔ‬ᑼ 2㧕‫ޔ‬෻ᔕᑼ (1)ߦ␜ߔᐔⴧ෻ᔕ߇ฝߦㅴ߻ߎߣߦ

ࠄߦ12ᤨ㑆ߩ෻ᔕࠍⴕߞߚ‫ޕ‬෻ᔕᓟ‫☸ޔ‬ሶࠍࠈㆊߒ‫ޔ‬ߥࠆ‫ޕ‬

᳓ߣࠛ࠲ࡁ࡯࡞ߢⶄᢙ࿁ᵞᵺࠍⴕߞߚᓟ‫ޔ‬ቶ᷷ߢੇ

2–[NH4]2TiF6+2H2O  TiO2+2NH4F+4HF(1)

῎ߐߖߚ‫ޕ‬ᓧࠄࠇߚ↢ᚑ‛ࠍ㔚᳇Ἱ㧔DenKen KDF

H3BO3+4HF  BF4+H3O++2H2O(2)

S90㧕ߢ10 ͠ min–1ߩ᣹᷷ㅦᐲߢ600 ͠߹ߢടᾲߒ‫ޔ‬㊄ዻ὇㉄Ⴎߩᓸ☸ሶߪ‫ޔ‬วᚑ߇◲නߢ‫㉄ޔ‬ಣℂߦߐࠄߦ3ᤨ㑆὾⚿ࠍⴕߞߚ‫ޕ‬ࠃߞߡ◲න߆ߟቢోߦಽ⸃ߐࠇࠆߎߣ߆ࠄ‫ޔ‬ᄙጀ㜞ಽሶ㔚⸃⾰⤑ߩ᦭ᯏࡑࠗࠢࡠࠞࡊ࠮࡞ࠍวᚑߔࠆ

 ․ᕈ⹏ଔ

ߚ߼ߩ࠹ࡦࡊ࡟࡯࠻ߣߒߡ‫ޔ‬ᐢߊ૶↪ߐࠇߡ߈ߚ 24)‫ޕ‬ᓧࠄࠇߚ↢ᚑ‛ߪ‫ޔ‬X ✢࿁᛬㧔 XRD‫ޔ‬Rigakuߘߩਛߢ߽ MnCO3 ߪ‫⸅ޔ‬ᇦ‫⏛ޔ‬ᕈ᧚ᢱ

25,26)‫ޔ‬27,28)XRD-DSC-X II㧕ߣ㔚⇇᡼಴⿛ᩏ㔚ሶ㗼ᓸ㏜㧔FESEM‫ޔ‬ల㔚ᳰ 29,30)߿ࠬ࡯ࡄ࡯ࠠࡖࡄࠪ࠲ 31-33)ߥߤߦ೑↪

Hitachi S-5200‫ޔ‬Japan㧕ࠍ↪޿ߡ⹏ଔߒߚ‫ޕ‬SEM ᷹ߢ߈ࠆ㉄ൻࡑࡦࠟࡦߩᦨ߽㊀ⷐߥේᢱߣߥࠆ‫ޔߦ․ޕ‬ቯࠍߔࠆ೨ߦ‫ ࠍ࡞ࡊࡦࠨޔ‬6 ᤨ㑆એ਄⌀ⓨੇ῎ߒ‫ޔ‬࠽ࡁ☸ሶ 34)‫࡯ࡗࠗࡢࡁ࠽ޔ‬35)‫☸ࡠࠢࠗࡑޔ‬ሶߦ⥋ࠆࠨࡦࡊ࡞ߦઃ⌕ߒߚṁᇦ߿᳓ࠍቢోߦ㒰෰ߒߚ‫ޕ‬㔚

MnCO3 ߩᄙ᭽ߥᒻᘒ

ߪ‫ޔ‬᭽‫ߥޘ‬ᒻᘒߩⶄว૕ࠍሶ ✢ߦ ࠃࠆ࠴ ࡖ࡯ ࠫࠕ࠶ ࡊ㒐 ᱛߩߚ ߼‫ ޔ‬Hitachi⵾ㅧߔࠆߚ߼ߩ࠹ࡦࡊ࡟࡯࠻ߣߒߡߩ೑↪ଔ୯߇

E-1030 ion sputter㧔15 μA, 10 Pa㧕ࠍ೑↪ߒߡ‫ࡦࠨޔ‬㜞޿‫ޕ‬

ࡊ࡞ߦ 5 nm ߩ Pt ⫳⌕ࠍⴕߞߚ‫ ޕ‬ㅘㆊ㔚ሶ㗼ᓸ㏜



㧔TEM㧕౮⌀ߪ‫ޔ‬JEOL JEM-3010 ࠍ೑↪ߒߡ‫ޔ‬200 kV

36)

㧞㧚ታ㛎

ߢⷰኤࠍⴕߞߚ‫ޕ‬TiO2 ࠦ࡯࠹ࠖࡦࠣ೨ᓟߩࠨࡦࡊ࡞  ⹜⮎ߩࡈ࡯࡝ࠛᄌ឵⿒ᄖಽశ㧔FTIR㧕᷹ቯߪ‫ޔ‬PerkinElmer⎫㉄ࡑࡦࠟࡦ᳓๺‛㧔MnSO4࡮H2O㧘Sigma-Aldrich

Spectrum100 FTIR spectrometer ࠍ↪޿ߡ 4000450

Co.㧕‫ޔ‬὇㉄᳓⚛࠽࠻࡝࠙ࡓ㧔NaHCO3㧘Kanto Chemical

cm–1 ▸࿐ߢⴕߞߚ‫ޕ‬MnCO3 ᓸ☸ሶߩࡊࡠ࠻ࡦๆ⌕Co. 㧕‫ࡓ ࠙ ࠾ ࡕ ࡦ ࠕ ㉄ ࡦ ࠲ ࠴ ࡠ ࠝ ࡞ ࡈ ࠨ ࠠ ࡋ ޔ‬ࠍ⺞ߴࠆߚ߼ߦ‫ޔ‬MnCO3 ᓸ☸ሶᷝടᓟߩ 0.1 M ߩ㧔[NH4]2TiF6㧘Mitsuwa Pure Chemicals㧕‫࠙ࡎߡߒߘޔ‬[NH4]2TiF6 ᳓ṁᶧߩ pH ᄌൻࠍ ISFET pH meter12

㧔KS701‫ޔ‬Shindengen㧕ࠍ↪޿ߡ᷹ቯߒߚ‫ޕ‬22,35)‫ߩ࡞࡯ࡁ࠲ࠛޕ‬ᷝടߦࠃࠅήᯏႮߩㆊ㘻๺ᐲ߇ടㅦߐࠇ‫ޔ‬ᩭ↢ᚑߣ⚿᥏ᚑ㐳߇ଦㅴߐߚߣ⠨߃ࠄࠇ ๆ⌕࠹ࠬ࠻ࠆ‫⚿ޔߡߞ߇ߚߒޕ‬᥏ᚑ㐳ߩೋᦼᲑ㓏ߢߪᣇะᕈߩ

὾⚿ᓟߦᓧࠄࠇߚ Mn2O3/TiO2 ⶄว૕ߩ‛ᕈࠍ⺞ߥ޿࠽ࡁ⚿᥏ߩ㓸ว૕߇ࠦࠕߦᒻᚑߐࠇ‫ߩߘޔ‬ᓟ‫ޔ‬ߴࠆߚ߼ߦ‫࡯࡞ࡉࡦ࡟࠴ࡔޔ‬᳓ṁᶧ㧔MB‫ޔ‬10 M㧕ࠦࠕߩᄖ஥ߦ᡼኿✢⁁ߦ⚿᥏߇ᚑ㐳ߔࠆ‫⚿ߩߘޕ‬ᨐ‫ޔ‬

ߦ 1.5 g L ߩỚᐲߦߥࠆࠃ߁ߦⶄว૕ࠍᷝടߒߚ‫ޕ‬☸ሶߩਛᔃㇱ߆ࠄᄖ஥ߦᚑ㐳ߒߚ MnCO3 ߩࡈ࡟࡯30 ⑽㑆ߩ MB ๆ⌕ߩᓟ‫ޔ‬㆙ᔃಽ㔌ߦࠃߞߡⶄว૕

ࠢߩᄙ㕙૕ߩ⚿᥏߇ᓧࠄࠇࠆ 38)‫ޕ‬ࠍᴉᲚߐߖ‫ޔ‬਄Ẵߺߩ⚡ᄖนⷞశಽశ᷹ቯࠍⴕߞߚ‫ޕ‬߹ ߚ ‫ ޔ‬ᓧ ࠄ ࠇ ߚ ⶄ ว ૕ ߩ Brunauer-Emmett-Teller  .2& ෻ᔕ–1

㧔BET㧕Ყ⴫㕙Ⓧ‫ޔ࠭ࠗࠨߩࠕࡐޔ‬ᄙሹᕈ⹏ଔࠍ⓸MnCO3 ᓸ☸ሶߣ[NH4]2TiF6 ߩ෻ᔕ㧔੍஻෻ᔕ㧕ߦ⚛ๆ⌕ⵝ⟎㧔BELLSORP mini-II‫ޔ‬Bell Japan㧕ࠍ↪޿ࠃࠆ☸ሶౝㇱߩᒻᘒᄌൻࠍ⺞ߴࠆߚ߼ߦ SEM ⷰኤߡⴕߞߚ‫ޕ‬ࠍⴕߞߚ‫ޕ‬Figure 2a ߆ࠄಽ߆ࠆࠃ߁ߦ‫ޔ‬2 ᤨ㑆ߩ੍஻෻ᔕᓟߩࠨࡦࡊ࡞ߢߪ‫☸ޔ‬ሶߩ⴫㕙߆ࠄ⚂ 200 nm㧟㧚⚿ᨐߣ⠨ኤ㔌ࠇߚߣߎࠈߦࠛ࠶࠴ࡦࠣߦࠃߞߡᒻᚑߐࠇߚᄙ  /P%1 ᓸ☸ሶߩᒻᘒᢙߩⓨ㓗߇⏕⹺ߢ߈ࠆ‫⥝ޕ‬๧ᷓ޿ߎߣߦ‫ޔ‬6 ᤨ㑆ߩ᳓ ́ ࠛ ࠲ ࡁ ࡯ ࡞ ᷙ ว ṁ ᇦ ᧦ ઙ ਅ ߢ MnSO4 ߣ੍஻෻ᔕᓟ‫ޔ‬Figure 2a ߢⷰኤߢ߈ߚ☸ሶߩࠦࠕㇱಽNaHCO3 ߩ෻ᔕ߆ࠄ MnCO3 ᓸ☸ሶࠍᓧߚ 24)‫ޕ‬Figure߇ቢోߦߥߊߥߞߡ޿ࠆߎߣ߇უࠇߚ☸ሶߩ SEM

1 ߦวᚑߐࠇߚ MnCO3 ᓸ☸ሶߩ SEM ௝ࠍ␜ߒ‫ࠛޔ‬௝߆ࠄ⏕⹺ߢ߈ࠆ㧔Figure 2b㧕‫ߣࠕࠦߥ߁ࠃߩߎޕ‬࠲ࡁ࡯࡞ᷝടߩ᦭ήߦࠃࠆᒻᘒߩ㆑޿߇⏕⹺ߢ߈ࠪࠚ࡞ߩ⇣ߥࠆࠛ࠶࠴ࡦࠣㅦᐲߪ‫ޔ‬MnCO3 ࠍ᭴ᚑࠆ‫ࠍ࡞࡯ࡁ࠲ࠛޕ‬ᷝടߒߚ႐ว‫ ⚂ޔ‬2.5 m ߩ⋥ᓘߔࠆࠦࠕߣࠪࠚ࡞ߩᒻᘒ⊛቟ቯᕈߦ⿠࿃ߔࠆ߽ߩ

ࠍ᦭ߔࠆ⃿⁁ߩ☸ሶ߇ᓧࠄࠇࠆߩߦኻߒߡ㧔Figureߣ್ᢿߐࠇࠆ 24)‫ޕ‬

1a㧕‫ࠍ࡞࡯ࡁ࠲ࠛޔ‬ᷝടߒߡ޿ߥ޿႐วߪ‫ޔ‬2 m ߩࠠࡘ࡯ࡆ࠶ࠢ⁁ߩ☸ሶ߇ᓧࠄࠇࠆ㧔Figure 1c㧕‫ޕ‬ Figure 2. SEM images of MnCO3 obtained withdifferent prereaction times: (a) 2 and (b) 6 h. Inset of ashows a magnified image of the area enclosed by theyellow rectangle.
[NH4]2TiF6 ߩ Ớ ᐲ ߅ ࠃ ߮ ੍ ஻ ෻ ᔕ ᤨ 㑆 ߪ ‫ޔ‬
MnCO3/TiO2 ⶄว૕ߩᒻᘒࠍ᳿ቯߔࠆ㊀ⷐߥࡄ࡜ࡔ
࡯࠲ߣߥࠆ‫ࠅࠃޕ‬᣿⏕ߥ᭴ㅧ⸃ᨆߩߚ߼ߦ‫ޔ‬12 ᤨ
Figure 1. SEM images of MnCO3 microspheres
prepared in (a, b) presence and (c, d) absence of ethanol.
Inset of b shows a whole image of the particle.
Figure 1b ߣ 1d ߩ㜞୚₸ߩ SEM ௝߆ࠄಽ߆ࠆࠃ߁ߦ‫ ߪ࡞࡯ࡁ࠲ࠛޔ‬MnCO3 ߩ⚿᥏ᚑ㐳ߦᄢ߈ߥᓇ㗀ࠍਈ߃ࠆⷐ࿃ߢ޽ࠆ‫ޔߪ࡞࡯ࡁ࠲ࠛޕ‬෻ᔕ♽ߩ⺃㔚₸ࠍᷫዋߐߖ‫ޔ‬ήᯏႮߩṁ⸃ࠍᛥ೙ߔࠆലᨐ߇޽ࠆ

13

㑆ߩ LPD ෻ᔕ߆ࠄᓧࠄࠇߚ MnCO3/TiO2 ⶄว૕ߩXRD‫ޔ‬FTIR ߅ࠃ߮ TEM ಽᨆࠍⴕߞߚ‫ޕ‬12 ᤨ㑆ߩ
LPD ෻ᔕ߆ࠄᓧࠄࠇߚࠨࡦࡊ࡞ߩ XRD ࡄ࠲࡯ࡦࠍ
Figure 3a ߦ␜ߔ‫ࠕࠦޕ‬㨺ࠪࠚ࡞᭴ㅧߩ MnCO3/TiO2
ⶄว૕㧔2 ᤨ㑆ߩ੍஻෻ᔕߣ 12 ᤨ㑆ߩ LPD ෻ᔕࠍⴕߞߚࠨࡦࡊ࡞㧕ߩ XRD ࡄ࠲࡯ࡦ߆ࠄ‫ޔ‬MnCO3 ߩࡇ࡯ࠢ߇ᄢ߈ߊᷫዋߒߡ޿ࠆߎߣ߇ಽ߆ࠆ‫ޕ‬ਛⓨ᭴フジコー技報−tsukuru No. ㅧߩ MnCO3/TiO2 ⶄว૕㧔6 ᤨ㑆ߩ੍஻෻ᔕߣ 12 ᤨᄌൻ߇޽ߞߚ‫ޔߒ߆ߒޕ‬TiO2 ࠦ࡯࠹ࠖࡦࠣߩᓟ‫ޔ‬500

㑆ߩ LPD ෻ᔕࠍⴕߞߚࠨࡦࡊ࡞㧕ߩ႐วߦߪ‫ޔ‬ᱴ㨪700 cm–1 ߣ 3200 cm–1 ઃㄭߦ TiO ߩિ❗ᝄേߣߤߩ MnCO3 ߩࡇ࡯ࠢ߇ᶖṌߒ‫ޔ‬25°ߦᣂߚߦࠕ࠽࠲

TiOH ߩ OH િ❗ᝄേߦ↱᧪ߔࠆࡉࡠ࡯࠼ߥࡃࡦ

࡯ࠬ TiO2 ߩࡇ࡯ࠢ߇㧔JCPDS No.84-1285㧕⃻ࠇߚ‫ޕ‬࠼߇⃻ࠇߚ‫ࠕࠦޔߦ․ޕ‬㨺ࠪࠚ࡞᭴ㅧߩ MnCO3/TiO2

ߒߚ߇ߞߡ‫ޔ‬MnCO3 ᓸ☸ሶߪ[NH4]2TiF6 ߣߩ੍஻෻

ⶄว૕ߪ‫ޔ‬ਛⓨ᭴ㅧߩⶄว૕ࠃࠅ 3450 cm–1 ઃㄭߩᔕ߿ߘߩᓟߩ LPD ෻ᔕߩ෻ᔕ႐ߣߒߡ௛߈‫ޔ‬TiO2

OH િ❗ᝄേ߇ᄢ߈޿ߎߣ߆ࠄ‫ޔ‬᳓ಽሶߩๆ⌕ߦߣⶄวൻߐࠇߚߎߣ߇ಽ߆ࠆ‫ޕ‬

MnCO3/TiO2 ⶄว૕ߩᲧ⴫㕙Ⓧ߇㑐ଥߒߡ޿ࠆߎߣ

 LPD ෻ᔕߦࠃߞߡᓧࠄࠇߚ MnCO3/TiO2 ⶄว૕߇ಽ߆ࠆ‫ޕ‬߅ࠃ߮ MnCO3 ᓸ☸ሶߩ FTIR ࠬࡍࠢ࠻࡞ࠍ Figure 3b

TiO2 ࠦ࡯࠹ࠖࡦࠣᓟߩࠦࠕ㨺ࠪࠚ࡞ᓸ☸ሶߩ SEM

ߦ␜ߒߚ‫ޕ‬MnCO3 ᓸ☸ሶߩ႐ว‫ޔ‬CO3 ߩિ❗ᝄേߣ TEM ௝ࠍ Figure 4 ߦ␜ߒߚ‫ޕ‬Figure 4a ߩ SEM ௝ߦ↱᧪ߔࠆࡇ࡯ࠢ߇ 1423‫ޔ‬862‫ޔ‬725 cm–1 ߦ߅޿ߡ߆ࠄ‫ޔ‬ᓧࠄࠇߚ MnCO3/TiO2 ⶄว૕ߪ⚂ 3.0 m ߩ⋥⏕⹺ߢ߈ࠆ‫ޕ‬
3450 cm ઃㄭߩࡉࡠ࡯࠼ߥࡃࡦ࠼ߪ‫ޔ‬ᓘࠍ᦭ߒ‫ޔ‬TiO2 ࠦ࡯࠹ࠖࡦࠣᓟߦ☸ሶࠨࠗ࠭߇Ⴧᄢ

MnCO3 ߦઃ⌕ߒߚ᳓ߩ OH ၮߩિ❗ᝄേࠍ⴫ߔ 34)‫ޕ‬ߒߡ޿ࠆߎߣ߇ಽ߆ࠆ‫‛ޔߦࠄߐޕ‬ℂ⊛ߦࠪࠚ࡞ࠍ

2––1⎕⎈ߒߚ☸ሶߩౝㇱ߆ࠄ⚂ 2 m ߩ⋥ᓘࠍ᦭ߔࠆᄙ
ሹᕈߩࠦࠕ߇ⷰኤߢ߈ࠆ‫ޔߚ߹ޕ‬MnCO3 ᓸ☸ሶߣᲧߴߡ⴫㕙߇Ṗࠄ߆ߦߥߞߡ޿ࠆߎߣ߇ಽ߆ࠆ
㧔Figure 4b㧕
‫ޕ‬Figure 4c ߣ 4d ߩ TEM ௝߆ࠄ⷗Ⓧ߽ࠄࠇߚࠪࠚ࡞ߩෘߐߪ⚂ 89 ± 14 nm ߢ޽ࠅ‫ޔ‬2 ᤨ㑆ߩ੍஻෻ᔕߩࠨࡦࡊ࡞ߢⷰኤߐࠇߚ⴫㕙ㄭߊߩⓨ㓗㧔Figure 2a㧕߇ 12 ᤨ㑆ߩ LPD ෻ᔕߦࠃࠅࠦࠕ㨺ࠪࠚ࡞᭴ㅧ߇ᓧࠄࠇߚ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬
Figure 3. (a) XRD patterns and (b) FTIR spectra of pure
MnCO3, core–shell MnCO3/TiO2 composite, and hollow
MnCO3/TiO2 composite microspheres. Inset of b shows
the respective spectra in the range 600–900 cm–1.
LPD ෻ᔕᓟ‫ޔ‬CO32–ߦ↱᧪ߔࠆિ❗ᝄേ߇ᷫ⴮ߒ‫ޔ‬․ߦ 6 ᤨ㑆ߩ੍஻෻ᔕߩࠨࡦࡊ࡞ߦ߅޿ߡ⪺ߒ޿
Figure 4. (a, b) SEM and (c) TEM images of core–shell
MnCO3/TiO2 composite. (d) Magnified TEM image ofthe area enclosed by the yellow square in c.

Figure 5 ߦਛⓨ᭴ㅧߩ MnCO3/TiO2 ⶄว૕ߩ SEM
ߣ TEM ௝ࠍ␜ߒߚ‫ޕ‬Figure 5a ߢߩ☸ሶߩ⴫㕙਄ߩዊߐߥⓣߪ‫[ޔ‬NH4]2TiF6 ᷝടᓟߦࡊࡠ࠻ࡦߦࠃߞߡ
ࠦࠕ߇ṁߌ‫☸ޔ‬ሶߩౝㇱ߆ࠄ CO2 ߇᡼಴ߐࠇࠆߎߣ
ߦࠃߞߡ૞ࠄࠇߚ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬უࠇߚᓸ☸ሶ

14

ߩ SEM ௝㧔Figure 5b㧕߆ࠄ☸ሶߩౝㇱ߇ቢోߦߥ

ߩṁ⸃ߦ᳓ṁᶧਛߩࡊࡠ࠻ࡦ߇૶ࠊࠇࠆߎߣߦ⿠

ߊߥߞߡ޿ࠆߎߣ߇⏕⹺ߢ߈‫☸ޔ‬ሶߩ⋥ᓘߪ⚂ 3.0

࿃ߔࠆ‫ߩߘޕ‬ᓟ‫ޔ‬ṁᶧߩ pH ߪ‫ޔ‬2 ᣣ㑆ߦᷰߞߡᓢ‫ޘ‬m‫ߩ࡞ࠚࠪޔ‬ෘߐߪ⚂ 246 ± 12 nm ߣ⷗Ⓧ߽ࠄࠇߚ‫ޕ‬

ߦ 5.6 ߹ߢჇടߔࠆ‫ߩߎޕ‬ੑᰴ⊛ߥ pH ᄌൻߪ‫ޔ‬෻߹ߚ‫ޔ‬Figure 5c ߩ TEM ௝߆ࠄ߽ਛⓨ᭴ㅧ߇૞ࠄࠇ

ᔕᑼ 1 ߣ 3 ߢ↢ᚑߐࠇࠆ NH4+ߣ HCO3–ࠗࠝࡦߩᐔ

ߚߎߣ߇⏕⹺ߢ߈ࠆ‫⥝ޕ‬๧ᷓ޿ߎߣߪ‫ࠕࠦޔ‬㨺ࠪࠚⴕ෻ᔕ㧔෻ᔕᑼ 4㧕ߦ㑐ㅪߔࠆ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬࡞᭴ㅧߣᲧセߒߡ‫ޔ‬ਛⓨ᭴ㅧߩࠪࠚ࡞߇ࠃࠅෘߊߥ

ߞߡ޿ࠆߎߣߢ޽ࠆ‫ޕ‬᜛ᄢߩ SEM ௝㧔Figure 5d㧕߆ࠄࠪࠚ࡞ߩਛᄩߦ⚦޿✢߇⏕⹺ߢ߈‫ߪࠇߎޔ‬MnCO3 ᓸ☸ሶߩ⴫㕙ࠍႺ⋡ߦᄖ஥ߣౝ஥߆ࠄߩ
TiO2 ߩࠦ࡯࠹ࠖࡦࠣጀ߇ᒻᚑߐࠇߚߎߣࠍⵣઃߌ
ࠆ‫ޕ‬



Scheme 1. Schematic of the Synthesis of Core–Shell
and Hollow MnCO3/TiO2 Composites: Cross-Sectional
Illustrations of MnCO3 Microsphere (a) before and (b,c) after Prereaction for 2 and 6 h with [NH4]2TiF6,
Respectively, and Their MnCO3/TiO2 Composites
Showing (d) Core–Shell and (e) Hollow Structures after
Sol–Gel Reaction for 12 h.

Scheme 1b ߦ␜ߔࠃ߁ߦ‫☸ ޔ‬ሶౝߦ᝝ᝒߐࠇߚࡊ
ࡠ࠻ࡦߪ‫ᦨޔ‬ೋߦ MnCO3 ᓸ☸ሶߩ⴫㕙ㄭߊߩౝㇱ
Figure 5. (a, b) SEM and (c) TEM images of hollow
MnCO3/TiO2 composite. (d) Magnified SEM image ofthe area enclosed by the yellow square in bࠍṁ⸃ߐߖ‫ߩߘޔ‬ᓟ‫ޔ‬᡼኿✢⁁ߩ MnCO3 ⚿᥏ߦᴪߞߡ᜛ᢔߒ‫ߦࡓ࠳ࡦ࡜ޔ‬㓸߹ߞߚ MnCO3 ࠽ࡁ⚿᥏ߩࠦࠕࠍṁ⸃ߒᆎ߼ࠆ‫ࠅࠃޔߦࠄߐޕ‬㐳޿੍஻෻ᔕ  ⶄว૕ߩวᚑ⚻〝ᤨ㑆ߪ‫ޔ‬ਛⓨ᭴ㅧߩᒻᚑࠍ⺃ዉߔࠆ㧔Scheme 1c㧕‫ޕ‬ࠦࠕ㨺ࠪࠚ࡞ߣਛⓨ᭴ㅧߩ MnCO3/TiO2 ⶄว૕ߩ↢ᚑ⚻〝ࠍ Scheme 1 ߦ␜ߔ‫੍ޕ‬஻෻ᔕߩ೨ߦ
MnCO3 ᓸ☸ሶߪ‫ޔ‬ౝㇱߦੑߟ⇣ߥࠆᒻᘒߩ⚿᥏ࠍ

2MnCO3+4H++4F  2Mn2++4F+2H++2HCO3
+

2NH4 +2HCO3



2NH3+2H2O+2CO2 (g)

(3)
(4)

᦭ߔࠆ‫[ޕ‬NH4]2TiF6 ࠍᷝടߔࠆߣ‫ޔ‬TiF6 ߪ MnCO3
2–

ᓸ☸ሶ⴫㕙਄ߩ Mn2+ࠗࠝࡦ㧔Ksp = 2.24×10–11㧕ߣ㍲

H3BO3 ࠍᷝടߔࠆߎߣߢ෻ᔕᑼ 1 ࠍടㅦߐߖࠆ

૕ࠍᒻᚑߒ‫⴫ޔ‬㕙ߦๆ⌕߇ᆎ߹ࠆ‫ߩߘޕ‬ᓟ‫ޔ‬ߎߣ߇ߢ߈ࠆ‫ޕ‬2 ᤨ㑆ߩ੍஻෻ᔕߣ 12 ᤨ㑆ߩ LPD[NH4]2TiF6 ߩട᳓ಽ⸃ߦࠃߞߡ↢ᚑߐࠇࠆ HF ߣߩ෻ᔕᓟߦࠦࠕߣࠪࠚ࡞߇ಽ㔌ߐࠇࠆ㧔Scheme 1d㧕‫ޕ‬෻ᔕ㧔෻ᔕᑼ 3㧕߇⿠ߎࠅ‫ࠕࠦޔ‬㨺ࠪࠚ࡞߹ߚߪਛ

߹ߚ‫ޔ‬6 ᤨ㑆ࠃࠅ㐳޿੍஻෻ᔕߣ 12 ᤨ㑆ߩ LPD ෻ⓨ ᭴ ㅧ ߩ MnCO3/TiO2 ⶄ ว ૕ ߇ ↢ ᚑ ߢ ߈ ࠆ ‫ޕ‬ᔕߦࠃߞߡ☸ሶߩਛ߇ᱴߤṁ⸃ߐࠇ‫ޔ‬ਛⓨ᭴ㅧߩ[NH4]2TiF6 ᳓ṁᶧߩ pH ߇ MnCO3 ᓸ☸ሶߩ᦭ήߦࠃ

MnCO3/TiO2 ⶄว૕߇ᒻᚑߐࠇࠆ㧔Scheme 1e㧕‫ޕ‬ߞߡ⇣ߥࠆߩߪ‫ߥ߁ࠃߩߎޔ‬෻ᔕࠍⵣઃߌࠆ㊀ⷐߥ⸽᜚ߣߥࠆ‫[ޕ‬NH4]2TiF6 ᳓ṁᶧߩೋᦼ pH ߪ 3.6 ߢ޽  /P%16K1ⶄว૕ߩ὾⚿ߞߚ߇‫ޔ‬MnCO3 ᓸ☸ሶࠍᷝടߔࠆߎߣߦࠃߞߡ 4.9

߹ߚ‫ޔ‬ᚒ‫ࠕࠦߪޘ‬㨺ࠪࠚ࡞ߣਛⓨ᭴ㅧߩ߹ߢჇടߔࠆ‫ߥ߁ࠃߩߎޕ‬ᄌൻߪ‫ޔ‬MnCO3 ᓸ☸ሶ

MnCO3/TiO2 ⶄว૕ߩ὾⚿ߦࠃࠆ⚿᥏ᕈ߅ࠃ߮ᒻᘒ

15

フジコー技報−tsukuru No. ߩᄌൻࠍ⺞ߴߚ‫ޕ‬὾⚿ᓟߩࠦࠕ㨺ࠪࠚ࡞ߣਛⓨ᭴ㅧ߅ࠃ߮ SEM ಽᨆߩ⚿ᨐ߆ࠄ߽὾⚿ᓟߦᓧࠄࠇߚᓸ

ߩ MnCO3/TiO2 ⶄว૕ࠍ Figure 6a ߣ 6b ߦ␜ߔ‫ޕ‬☸ሶ߇ᾲಣℂߦࠃߞߡ቟ቯߥ᭴ㅧߦᄌࠊߞߚߎߣ

߇⏕⹺ߢ߈ࠆ‫ޕ‬  ๆ⌕․ᕈ὾⚿ᓟߦᓧࠄࠇߚࠦࠕ㨺ࠪࠚ࡞ߣਛⓨ᭴ㅧߩ
Mn2O3/TiO2 ⶄว૕ߩ‛ᕈࠍ⺞ߴࠆߚ߼ߦ‫⚛⦡ޔ‬ಽሶߩๆ⌕ታ㛎ࠍⴕߞߚ‫ޕ‬Figure 8 ߦࠦࠕ㨺ࠪࠚ࡞ߣਛⓨ᭴ㅧߩ Mn2O3/TiO2 ⶄว૕㧔ߘࠇߙࠇ 1.5 g L–1㧕ࠍ↪
޿ߚๆ⌕ታ㛎೨ᓟߩ 10 M ߩ MB ߩ⚡ᄖนⷞๆ෼ࠬ
ࡍࠢ࠻࡞ࠍ␜ߔ‫ޕ‬MB ṁᶧߦߘࠇߙࠇߩⶄว૕ࠍᷝ
ടߒ‫ޔ‬30 ⑽㑆ߩᝄߣ߁ߛߌߢ MB ߩๆ෼ࠬࡍࠢ࠻
࡞߇ᄢ᏷ߦᷫዋߒ‫ߦ․ޔ‬ਛⓨ᭴ㅧߩⶄว૕߇ࠃࠅᄢ

Figure 6. XRD patterns of calcined (a) core–shell and(b) hollow MnCO3/TiO2 composites.὾⚿ᓟ‫ޔ‬㕖᥏⾰ TiO2 ߪࠕ࠽࠲࡯ࠬ TiO2㧔JCPDS
No.84-1285㧕ߦ‫ޔ‬MnCO3 ߪ -Mn2O3 ߦᄌൻߒߚ‫ޕ‬ਛⓨ᭴ㅧߩ MnCO3/TiO2 ⶄว૕ߩ႐ว‫ޔ‬600 °C ߢ 3 ᤨ㑆ߩᾲಣℂࠍⴕߞߚ႐ว‫ޔ‬-Mn2O3 ߩࡇ࡯ࠢߪ߶ߣ
ࠎߤ⃻ࠇߥ޿‫ޕ‬Figure 7 ߆ࠄಽ߆ࠆࠃ߁ߦ‫ ޔ‬ੑߟߩ὾⚿ߐࠇߚࠨࡦࡊ࡞ߪ὾⚿೨ᓟߦ߅޿ߡᒻᘒ⊛ᄌ߈޿ᄌൻࠍ␜ߒߚ‫ޕ‬Figure 8 ߩᝌ౉౮⌀߆ࠄๆ⌕ታ㛎೨ᓟߩ MB ߩ⦡ߩᄌൻࠍ⏕⹺ߔࠆߎߣ߇ߢ߈ࠆ‫ޕ‬MB ߩๆ⌕ኈ㊂ࠍ 664.5 nm ߢߩๆశᐲࠍ↪޿ߡᲧセߒߚߣߎࠈ‫ࠕࠦޔ‬㨺ࠪࠚ࡞᭴ㅧߩ Mn2O3/TiO2 ⶄว૕ߪ 77㧑‫ޔ‬ਛⓨ᭴ㅧߩ Mn2O3/TiO2 ⶄว૕ߪ 95㧑ߩᷫዋࠍ␜ߒߚ‫ࠕࠦޔߡߞ߇ߚߒޕ‬㨺ࠪࠚ࡞ߣਛⓨ᭴ㅧߩ Mn2O3/TiO2 ⶄว૕ߪߘࠇߙࠇ 5.2 ߣ 6.4 mol g–1
ߩ MB ๆ⌕ኈ㊂ࠍ᦭ߔࠆߎߣߦߥࠆ‫ޕ‬ൻߪᱴߤ⷗ࠄࠇߥ޿‫ޔߛߚޕ‬὾⚿ᓟߦࠦࠕ㨺ࠪࠚ࡞ⶄว૕ߩࠦࠕߩ⴫㕙ߪ࠙࠾ߩࠃ߁ߥ᭴ㅧߣߥࠅ‫ޔ‬ಳಲ߇ࠃࠅჇߒߡ޿ࠆ‫ޔߚ߹ޕ‬὾⚿ᓟߩ↢ᚑ‛ߩ⦡߇᣿ࠆ޿⨥⦡߆ࠄᥧⶊ⦡ߦᄌൻߒߚ‫ޕ‬

Figure 8. UV–vis absorption spectral changes of MB(10 M in water) after 30 s incubation with Mn2O3/TiO2composites (1.5 g L–1). Inset shows a photographshowing colorimetric image of MB (1) before and after
adsorption test with (2) core–shell and (3) hollow
composites.
Figure 7. SEM images of Mn2O3/TiO2 composites
obtained after calcination at 600 °C for 3 h: (a, b)
core–shell structure and (c, d) hollow structure.
ߎࠇߪ‫↢ޔ‬ᚑߐࠇߚⶄว૕ߩᓸ☸ሶߦᱷሽߔࠆ
MnCO3 ߇ Mn2O3 ߦᄌࠊߞߚߎߣߦᗧ๧ߔࠆ‫ޕ‬XRD

৻ᣇ‫ࠕࠦޔ‬㨺ࠪࠚ࡞᭴ㅧߩ Mn2O3/TiO2 ⶄว૕ߣਛⓨ᭴ㅧߩ Mn2O3/TiO2 ⶄว૕ߩᲧ⴫㕙Ⓧߪ‫ޔ‬BET ᷹ቯ߆ࠄߘࠇߙࠇ 83.6 ߣ 21.4 m2 g–1 ߣ⷗Ⓧ߽ࠄࠇߚ‫ޕ‬ਛⓨ᭴ㅧߩⶄว૕߇ૐ޿୯ࠍ␜ߒߡ޿ࠆߦ߽߆߆
ࠊࠄߕ‫ࠕࠦޔ‬㨺ࠪࠚ࡞ߩⶄว૕ࠃࠅఝࠇߚๆ⌕․ᕈ
16ࠍ␜ߔ‫ⶄޔߪࠇߎޕ‬ว૕ߦᱷሽߔࠆ -Mn2O3 ߣ TiO2
ߩ⋧ኻ㊂߇㑐ଥߒ‫߇ࠄࠇߘޔ‬ਔᣇߩⶄว૕ߩ⴫㕙㔚⩄ߦᓇ㗀ࠍਈ߃ߡ޿ࠆߚ߼ߢ޽ࠈ߁‫ޕ‬ᱷᔨߥ߇ࠄ‫ޔ‬ߎߩᲑ㓏ߢߪ‫ߥ߁ࠃߩߘޔ‬ๆ⌕᜼േߩ⹦⚦ࠍ⺑᣿ߔࠆߩߦචಽߥታ㛎࠺࡯࠲߇ߥ޿‫⃻ޕ‬࿷‫ߥ߁ࠃߩߎޔ‬․⇣⊛ߥๆ⌕᜼േࠍ⺑᣿ߔࠆߚ߼ߩㅊടታ㛎ߣశ⸅ᇦᵴᕈߩ⹏ଔߚ߼ߩ⎇ⓥࠍㅴ߼ߡ޿ࠆ‫ޕ‬㧠㧚⚿⺰ᧄ⎇ⓥߢᚒ‫ޔߪޘ‬MnCO3 ᓸ☸ሶࠍ࠹ࡦࡊ࡟࡯࠻
ߣߔࠆࠦࠕ㨺ࠪࠚ࡞߹ߚߪਛⓨ᭴ㅧߩ MnCO3/TiO2
ⶄว૕ߩᣂߒ޿⵾ㅧᣇᴺࠍ⚫੺ߒߚ‫ޕ‬2 Ბ㓏ߩ LPDࡊࡠ࠮ࠬ߆ࠄวᚑߐࠇߚ MnCO3/TiO2 ⶄว૕ߩ᭴ㅧ
ߪ‫ޔ‬೨㚟૕ߢ޽ࠆ[NH4]2TiF6 ߣߩ੍஻෻ᔕߩ෻ᔕᤨ
㑆ࠍ೙ᓮߔࠆߎߣߦࠃࠅน⢻ߢ޽ߞߚ‫ޔߚ߹ޕ‬὾⚿ᓟߦߪ‫ޔ‬὾⚿೨ߣ߶߷ห᭽ߥᒻᘒࠍ⛽ᜬߒߥ߇ࠄ
-Mn2O3 ߣࠕ࠽࠲࡯ࠬ TiO2 ߩᣂߒ޿ⶄว૕ߦᄌൻ
ߒ‫⚛⦡ߥ߁ࠃߩ࡯࡞ࡉࡦ࡟࠴ࡔޔ‬ಽሶߦ㜞޿ๆ⌕․ᕈࠍ␜ߒߚ‫੹ޕ‬ᓟ‫ⶄߩࠄࠇߎޔ‬ว૕ߩᒻᘒ⊛․ᕈߦၮߠ޿ߚൻቇ‛⾰ߩๆ⌕‫ޔ‬శ⸅ᇦ‫ޔ‬㔚ᭂ᧚ᢱߥߤߩ
᭽‫ߥޘ‬ᔕ↪߇ᦼᓙߢ߈ࠆ‫⎇ᧄޕ‬ⓥᚻᴺߪ㕖Ᏹߦ◲ଢ߆ߟ᳢↪⊛ߢ‫‛ߩ․⁛ޔ‬ℂൻቇ⊛․ᕈࠍ᦭ߔࠆ᭽‫ޘ‬ߥ㉄ൻ࠴࠲ࡦⶄว૕ߩ㐿⊒ߦᔅⷐߥᣇᴺ⺰ࠍឭଏ
ߔࠆ‫ޕ‬


⻢ㄉ
ᧄ ነ Ⓜ ߩ ర ߣ ߥ ࠆ ACS Applied Materials &Interfaces (2014, 6, 5764, dx.doi.org/10.1021/am404052p) ⚕ߦ⸶಴

⸵นߩ⻢ᗧࠍ⴫ߔࠆ‫ޕ‬



ෳ⠨ᢥ₂
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