ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

2013B3320, 2014A3320,2014B3320,2015A3320

BL08B2In-situ XAFS/SAXS ಉ࣌ଌఆʹΑΔ Au φϊཻࢠੜ੒աఔղੳ
Formulation Process Analysis of Au Nano-particle by Coupled
In-situ XAFS and SAXS౦‫ޫ ޱ‬੖ɼࡔຊ ௚‫ل‬
Mitsuharu Higashiguchi, Naoki Sakamoto1ѴԽ੒‫ࣜג‬ձࣾ
Asashi Kasei Corporation֓ཁɿӷ૬͔Βͷφϊཻࢠͷੜ੒աఔΛධՁ͢Δख๏ͱͯ͠ɼՁ਺มԽͱཻࢠ੒௕աఔΛ XAFS/SAXS ಉ࣌ଌఆʹͯ‫͢࡯؍‬Δख๏ཱ֬Λ໨ࢦͨ͠ɽHAuCl4 ༹ӷͷؐ‫ʹݩ‬ΑΔ Au φϊཻࢠੜ੒Λྫͱͯ͠ɼۚଐ΁ͷՁ਺มԽɼཻࢠੜ੒ɼ༹ӷͷ‫ͨݟ‬໨ͷมԽ͕ରԠͨ͠Ұ࿈ͷղੳ݁ՌΛऔಘ͢Δ͜ͱ͕Ͱ͖ɼφϊཻࢠͷੜ੒աఔΛ၆ᛌ͢Δଌఆٕज़ͷཱ֬Λୡ੒ͨ͠ɽΩʔϫʔυɿφϊཻࢠɼXAFSɼSAXSɼin-situഎ‫ڀݚͱܠ‬໨తࠓճɼۚଐφϊཻࢠͷதͰ΋ɼଟ͘ͷใࠂྫ͕͋Δۚଐφϊཻࢠ͸ɼൺද໘ੵ͕‫ۃ‬Ίͯେ͖͍͜ͱ΍ɼిࢠͷด͡ࠐΊʹ༝དྷͨ͠ྔࢠޮՌʹΑΓ௨ৗͷࡐྉͱ͸ҟͳΔޫֶಛੑ౳Λࣔ͢͜ͱ͔Βɼ৮ഔɼృྉɼߏ଄վ࣭ࡎɼిࢠࡐྉ౳༷ʑͳ෼໺Ͱ༻͍ΒΕ͍ͯ
Δ [1]ɽۚଐφϊཻࢠͷಛ௃ͱͯ͠ɼཻ‫ܘ‬΍෼෍ɼϞϧϑΥϩδʔͷҧ͍͕෺ੑʹ௚݁͢ΔͨΊɼ͜ΕΒཻࢠಛੑͷਫ਼ີ੍‫ۀ޻͕ޚ‬తʹॏཁͳ՝୊ͱͳΔɽۚଐφϊཻࢠ͸ӷ૬๏΍‫ؾ‬૬๏Ͱ࡞ΒΕΔ͕ [1]ɼӷAu φϊཻࢠͷੜ੒աఔΛར༻͠ɼXAFS/SAXS ಉ࣌ଌఆʹΑΓɼφϊཻࢠͷੜ੒աఔʹॏཁͳؐ‫ࢠཻͱݩ‬੒௕աఔΛಉ࣌ʹ‫͢࡯؍‬Δख๏ͷཱ֬Λ໨ࢦͨ͠ɽຊ
ख๏͸ɼAu Ҏ֎ͷφϊཻࢠ΁ͷల։΍ɼՁ਺มԽͱߏ଄มԽ͕‫͜ى‬Δ৮ഔ൓Ԡʹ΋ల։͕‫·ࠐݟ‬ΕΔͨ
Ίɼଟ͘ͷ੡඼։ൃʹ‫د‬༩Ͱ͖Δͱ‫ظ‬଴͍ͯ͠Δɽ࣮‫ݧ‬૬๏͸େྔੜ࢈ʹద͓ͯ͠Γɼ·ͨೱ౓΍Թ౓ͷ؅ཧ

Au φϊཻࢠͷ࡞੒͸ɼҰൠతʹ༻͍ΒΕ͍ͯΔɼ

͕༰қͰ͋ΔͨΊ޿͘༻͍ΒΕ͍ͯΔɽӷ૬๏ͷத

HAuCl4 ༹ӷʹΫΤϯࢎφτϦ΢ϜΛՃ͑ɼؐ‫ʹݩ‬ΑͰ΋ؐ‫ࡎݩ‬Λ༻͍ͯɼۚଐΠΦϯΛ࠶ੳग़ͤ͞Δؐ‫ݩ‬Γੳग़ͤ͞Δํ๏Λબ୒ͨ͠ɽHAuCl4 ༹ӷͱΫΤϯ๏͸ɼख๏ͷ؆ศ͔͞Β޻‫ۀ‬తʹ΋ར༻͠΍͍͢ɽۚࢎ༹ӷͷೱ౓͸ɼա‫ڈ‬ͷྨࣅͷଌఆͷจ‫ݙ‬Λࢀߟʹͦଐφϊཻࢠͷੜ੒͸ɼۚଐΠΦϯ༹ӷ΁ؐ‫ࡎݩ‬Λ౤ೖΕͧΕɼ0.25 mmol/L ͱ 2.5 mmol/L ͱͨ͠ [2]ɽࢼ‫ʹ͙͢ޙ‬͸‫͜ى‬Βͣɼ༠ಋ‫ؒظ‬Λ‫ࢠཻͯܦ‬ͷੜ੒͕ੜྉͷௐ੔͸ɼ์ࣹޫϋον֎Ͱߦ͍ɼ༹྆ӷΛόΠΞ

͡Δɽ༠ಋ‫ʹظ‬͸ɼۚଐΠΦϯͷؐ‫֩ͱݩ‬ͷੜ੒͕‫ى‬ϧළதͰྑࠞ͘߹ͤͨ͞‫ޙ‬ɼφ2mm ͷੴӳΩϟϐϥ͍ͬͯ͜Δͱߟ͑ΒΕΔ͕ɼ੡଄ͰͷධՁ͸ɼੜ੒‫ޙ‬ϦʔʹೖΕଌఆʹ‫ͨ͠ڙ‬ɽࢼༀྨ͸ɼࠞ߹௚લ·ͰྫྷͷۚଐφϊཻࢠͰߦ͏ͨΊɼ༠ಋ‫ؔ͢ʹظ‬Δ஌‫ݟ‬͸গଂ͓͖ͯ͠ɼࠞ߹͸ࣨԹͰߦ͍ͬͯΔɽͳ͍ɽͦͷͨΊɼ৽‫ن‬ͷཻࢠಛੑΛ࣋ͭɼۚଐφϊཻ

XAFS/SAXS ಉ࣌ଌఆ͸ɼฌ‫ݝݿ‬ϏʔϜϥΠϯࢠΛ੡଄͢Δࡍʹ͸ɼͦͷ౎౓ɼ੡଄৚݅ͷ‫ݟ‬௚͕͠

BL08B2 ͷୈ 2 ϋονʹ࣮ͯࢪͨ͠ɽFig. 1 ʹଌఆͷඞཁͱͳΔɽ༠ಋ‫ظ‬Λཧղ͠ɼཻࢠͷੜ੒ɼ੒௕͕ͲηοτΞοϓਤΛࣔ͢ɽࢼྉԹ౓͸ࣨԹʢ25◦ Cʣͱ͠ͷΑ͏ͳλΠϛϯάͰ‫͍ͯͬ͜ى‬Δ͔஌Δ͜ͱ͕Ͱ͖

ͨɽXAFS ଌఆ͸ɼSi(111)-2 ݁থ෼ޫ‫ث‬Λ࢖༻͠ɼAu-Ε͹ɼࢼ࡞࣌ؒͷ୹ॖʹ‫د‬༩Ͱ͖Δͱ‫ظ‬଴͞ΕΔɽLIII ୺ (11920 eV) ʹͯ‫ޫܬ‬๏ͷ Q-XAFS Λߦͬͨɽ‫ ޫܬ‬X ઢͷ‫ݕ‬ग़‫ʹث‬͸ Lytle ‫ݕ‬ग़‫ث‬Λ༻͍ͨɽSAXS– 15 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)

Fig. 1. Schematic view of coupled in-situ XAFS andSAXS experimental set-up.

ଌఆ͸ɼࢼྉ͔ΒͷΧϝϥ௕ 1940 mm ͱ͠ɼ‫ݕ‬ग़‫ث‬ʹ͸ PILATUS-100k Λར༻ͨ͠ɽAu ‫ٵ‬ऩ୺ͷӨ‫ڹ‬Λආ͚ΔͨΊɼଌఆ͸‫ٵ‬ऩ୺ΑΓΤωϧΪʔͷ௿͍

11810 eVʢ೾௕ɿ0.105 nmʣͱͨ͠ɽಘΒΕͨ̎࣍‫ ݩ‬SAXS ύλʔϯ͸ಁա཰ɼۭηϧࢄཚิਖ਼Λ͓͜ͳ͏ͱͱ΋ʹɼԁ‫؀‬ฏ‫ʹۉ‬ΑΓ̍࣍‫ݩ‬Խͯ͠ղੳʹ‫͠ڙ‬ͨɽۭηϧࢄཚͱͯ͠͸ະ൓ԠͷӷͷࢄཚΛ༻͍ͨɽຊ࣮‫Ͱݧ‬͸ۚφϊཻࢠੜ੒ʹ൐͍ɼ༹ӷ͕ೱ͍੺৭ΛFig. 2.

Normalized Au-LIII -edge X-ray absorp-tion spectra during formulation process of Au nanoparticle.

ఄͯ͘͠Δɽͦ͜ͰɼੴӳΩϟϐϥϦʔʹࢼྉΛηοτͨ͠‫ʹޙ‬όΠΞϧϏϯʹ࢒༹ͬͨӷʹ͍ͭͯϏσΦ͓Γۚଐ·Ͱؐ‫͕ݩ‬ਐΜͰ͍Δͱਪଌ͞Εͨɽؐ‫ݩ‬աࡱӨΛߦ͍ɼ໨ࢹͰண৭͢Δ࣌ؒΛ‫ܭ‬ଌͨ͠ɽ·ͨɼఔΛ͞Βʹৄ͘͠‫ݟ‬ΔͨΊʹɼ‫ٵ‬ऩ୺ͷ‫࣌ܦ‬มԽΛಋ

XAFS/SAXS ಉ࣌ଌఆʹ‫ͨ͠ڙ‬ੴӳΩϟϐϥϦʔதग़ͨ͠ɽ‫ٵ‬ऩ୺ͷҐஔ͸ɼεϖΫτϧ‫֨ن‬Խ‫ޙ‬ͷΤοͷ༹ӷͷ৭ͷมԽʹ͍ͭͯ΋ΧϝϥʹΑΓϞχλʔδδϟϯϓͷ‫ ౓ڧ‬0.5 ͱͳΔΤωϧΪʔͰఆٛͨ͠ɽ

ͨ͠ɽ

Fig. 3 ʹ Fig. 2 ͷεϖΫτϧ͔Βಋग़ͨ͠‫ٵ‬ऩ୺Τωຊ࣌෼ׂ XAFS/SAXS ಉ࣌ଌఆʹ͓͚ΔଌఆαΠϧΪʔͷ‫࣌ܦ‬มԽΛࣔ͢ɽԣ࣠͸༹ӷΛࠞ߹͔ͨ࣌͠Ϋϧ͸ɼ3.5 ෼Ͱ͋ΔɽԼ‫֤ʹه‬αΠΫϧͰ͸ҎԼͷΒͷ࣌ࠁͱ͍ͯ͠Δɽ࠷ऴతʹۚଐ·Ͱؐ‫͕ݩ‬ਐΉͱॱʹࢼྉͷ֎‫؍‬ɼSAXSɼXAFS ଌఆΛ࣮ࢪͨ͠ɽͯ͠ɼՁ਺มԽ͕Ұఆͱͳͬͨͱ͜ΖΛ+0 ՁɼAuClඪ४ࢼྉͷ‫ٵ‬ऩ୺ҐஔΛ+1 Ձͱͯ͠ਤʹࣔͨ͠ɽࠞ

1 ༹ӷͷը૾ࡱӨ

2 XAFS ։࢝ΤωϧΪʔʹͯ SAXS Λ 10 ඵ࿐ޫͰ߹͔Βͷ࣌ؒΛθϩʹ֎૷ͯ͠ɼ͓Αͦ 1 Ձ෼ɼՁ਺

3 Q-XAFS ଌఆ‫ޙ‬Ҏ߱͸ɼ‫ٵ‬ऩ୺Ґஔ͸΄΅ҰఆͰɼͦΕҎ্ؐ‫͕ݩ‬ଌఆมԽ͍ͯ͠Δͱਪଌ͞Εͨɽ·ͨɼࠞ߹͔Β 50-60 ෼ࠞ߹͔Βଌఆ·ͰͷλΠϜϥά͕ൃੜ͢ΔͨΊɼผ్ਐߦ͍ͯ͠ͳ͍ͱਪଌ͞ΕΔɽ‫ݪ‬ྉͷ HAuCl4 ͸ɼ+3࣌ࠁΛ‫ܭ‬ଌ݁͠Ռʹ൓ө͍ͤͯ͞Δɽ

ՁͰ͋ΔͨΊɼࠞ߹‫ʹ͙͢ޙ‬+1 Ձ·Ͱ‫͕ݩؐʹܹٸ‬ਐΈɼͦͷ‫ޙ‬؇΍͔ʹ+0 Ձʹ޲͚ؐ‫͕ݩ‬ਐΉͷͰ͸ͳ͍͔ͱਪଌ͞ΕΔɽ݁Ռ͓Αͼߟ࡯

Fig. 2 ʹ Au φϊཻࢠੜ੒աఔͷ Au-LIII ୺ XAFSεϖΫτϧͷॏͶॻ͖Λࣔ͢ɽ੺͔Β੨΁ͱ͕࣌ؒ‫ܦ‬ա͍ͯ͠Δɽ໼ҹͰࣔͨ͠ɼ11923 eV ෇ۙͷ Au-LIII‫ٵ‬ऩ୺εϖΫτϧϐʔΫ͕ɼ࣌ؒͱ‫ݮʹڞ‬গ͍ͯ͠Fig. 4 ʹ Au φϊཻࢠੜ੒աఔʹ͓͚Δ SAXS ϓϩϑΟʔϧมԽΛࣔ͢ɽԣ࣠͸ࣜ 1 Ͱද͞ΕΔࢄཚϕΫτϧͷઈର஋Ͱ͋Δɽͳ͓ɼθ ͸ Bragg ֯ɼλ ͸ Xઢ೾௕Ͱ͋Δɽ༷͘ࢠ͕‫؍‬ଌ͞Ε͍ͯΔɽࢀরࢼྉ (HAuCl4 (Au3+ )ɼ

AuCl(Au1+)ɼAu ഩ (Au0+)) ͷଌఆ͔ΒɼAu-LIII ‫ٵ‬ऩ୺εϖΫτϧϐʔΫ͸ɼߴՁ਺΄ͲӶ͘ɼҰํͰۚଐʹͳΔͱফࣦ͢Δ܏޲͕‫ݟ‬ΒΕͨɽͦͷͨΊɼFig.

1 ͷมԽ͸ɼؐ‫ݩ‬աఔΛ‫͍ͯݟ‬Δͱߟ͑ΒΕΔɽ·ͨɼ‫࣌ܦ‬มԽͷ࠷ऴεϖΫτϧ͸ɼAu ഩͱ΄΅Ұகͯ͠q = 4π sin θ/λ(1)൓Ԡ։࢝‫ޙ‬ɼ40 ෼ఔ౓·Ͱ͸΄ͱΜͲࢄཚ͕‫؍‬ଌ͞Ε͓ͯΒͣɼSAXS Ͱଊ͑ΒΕΔΑ͏ͳφϊߏ଄͸‫ܗ‬੒͞Ε͍ͯͳ͍ͱߟ͑Β͑ΔɽҰํɼ40 ෼Ҏ߱ Au φϊཻࢠ༝དྷͷࢄཚ‫౓ڧ‬ͷ૿େ͕‫؍‬ଌ͞Ε͍ͯΔɽͳ͓ɼ– 16 –ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒ՌूFig. 3.

Time-dependent absorption-edge energyof Au-LIII , in which energy of Au-foil(+0) andAuCl(+1) are also represented as references.

Fig. 4. SAXS profiles during formulation process ofAu nano-particle.

ΑΓৄ͘͠ SAXS ϓϩϑΟʔϧมԽΛ‫ݟ‬Δͱ 40 ෼Ҏ߱ 47 ෼ఔ౓·Ͱখ֯ྖҬͷࢄཚ͕૿Ճͨ͠‫ޙ‬ɼ54 ෼ఔ౓·ͰҰ౓ࢄཚ‫ݮ͕౓ڧ‬গ͍ͯ͠Δɽ͞Βʹɼͦͷ‫ࢄͼ࠶ޙ‬ཚ‫౓ڧ‬͸૿Ճʹస͡Δ͕ɼࢄཚγϣϧμʔͷҐஔ͸ 40-51 ෼ͷ΋ͷΑΓ΋޿֯ʹଘࡏ͍ͯ͠Δɽ‫ܗ‬੒͞ΕΔ Au φϊཻࢠͷαΠζΛఆྔతʹߟ࡯͢ΔͨΊʹɼFig. 4 ͷ 40 ෼Ҏ߱ͷ SAXS ϓϩϑΟʔϧΛࣜ̎Ͱද͞ΕΔ൒‫ܘ‬෼෍Λߟྀͨ͠ϥϯμϜ഑޲γϦϯμʔߏ଄Λ࣋ͭ‫ࢠཱཻݽ‬ͷཧ࿦ࢄཚࣜͰϑΟοςΟϯά͠ɼ֤छύϥϝʔλΛಘͨɽ൒‫ܘ‬ͷ෼෍͸ମੵ෼
཰͕ Schultz-Zimm ෼෍ʹै͍ͬͯΔͱԾఆͨ͠ɽͳ͓ɼ∆ρe ͸༹ഔͱཻۚࢠͷిࢠີ౓ࠩɼN ͸ཻࢠͷ਺ີ౓ɼrɼl ͸γϦϯμʔʢͻ΋ʣঢ়ߏ଄ͷ൒‫ͱܘ‬௕͞ɼσ ͸൒‫ ܘ‬r ͷඪ४ภࠩɼJ1 ͸̍࣍ͷϕοηϧؔ

ͳ͓ɼFig. 4 ͷ SAXS ϓϩϑΟʔϧ͸‫ٿ‬ঢ়ཻࢠΛԾఆͨ͠ཧ࿦ࢄཚࣜͰ͸͏·͘ϑΟοςΟϯάͰ͖ͣɼͻ΋ঢ়ߏ଄ΛԾఆͨ͠΄͏͕Α࣮͘ଌ SAXS ϓϩϑΟʔϧΛ࠶‫͖ͨͰݱ‬ɽFig. 4 ʹ͸ࣜ (2) ʹΑΓߦͬͨϑΟοςΟϯάͷ݁Ռʹ͍ͭͯ΋߹Θ͍ͤͯࣔͯ͠Δɽ࣮ࡍͷཻࢠ‫ܗ‬ঢ়ʹ͍ͭͯిࢠ‫ݦ‬ඍ‫ʹڸ‬ΑΔ֬ೝ͸ߦ͍ͬͯͳ͍͕ɼจ‫Ͱݙ‬͸ͻ΋ঢ়ͷߏ଄͕‫ܗ‬੒͞ΕΔྫ΋ใࠂ͞Ε͓ͯΓ [3]ɼ͜͜Ͱ͸ͻ΋ঢ়ߏ଄ΛԾఆͯ͠ղੳ
Λߦͬͨɽ·ͨɼAu φϊཻࢠͷྔʢମੵʣͷࢦඪͱͯ͠ɼࣜ (3) Ͱද͞ΕΔ Invariant Q Λ‫ͨ͠ࢉܭ‬ɽͳ͓ɼੵ෼ൣғ͸ɹ 0.07 < q < 1.2 nm−1 ͱͨ͠ɽಛʹখ֯ྖҬͷੵ෼ൣғ͕ෆे෼͕ͩɼੜ੒ͨ͠ Au φϊཻࢠͷྔʢମੵʣͷ܏޲͸௥͑Δͱߟ͑ΒΕΔɽ͜͏ͯ͠‫͞ࢉܭ‬Εͨͻ΋ঢ়ߏ଄ͷฏ‫ۉ‬௚‫ ܘ‬dɼ‫ͼٴ‬਺ɺSi(x) ͸ੵ෼ਖ਼‫͋Ͱ਺ؔݭ‬Δɽl  r ΛԾఆͯ͠

Invariant Q ͷ࣌ؒมԽΛ Fig. 5 ʹࣔ͢ɽ ൓Ԡ‫ ޙ‬40

 ∞(2)

͍Δɽ

I(q)2=F (q, r, l)=P (r)=P  (r)=M=∆ρ2e NP (r)F 2 (q, r, l)dr0221 − cos(ql) J1 (qr)8(πr2 l)Si(ql)−
ɹqlqlqr
P  (r)/V (r)ɹP  (r)/V (r)dr


MMM
M −1r
exp−r
ɹ
r0
Γ(M )r0M

σ −0.5 ɹ– 17 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)૿Ճ͍ͯ͠ΔՄೳੑ΋͋Δɽd ͱ Q ͷ࣌ؒมԽ͸ɼ40෼Ҏ߱ʹ‫ܗ‬੒͞Εͨφϊཻࢠ͸‫ߏूڽ‬଄Λ‫ܗ‬੒͓ͯ͠ΓɼͦΕ͕Ұ౓ɼ෼྾ͨ͠‫ޙ‬ɼ࠶ͼ੒௕͢Δͱ͍͏աఔΛ͍ࣔͯ͠Δͷ͔΋͠Εͳ͍ɽ40 ෼Ҏ߱͸ɼՁ਺มԽ͕΄΅ۚଐͱͯ͠Ұఆʹͳ͍ͬͯΔ͜ͱ͔Βɼۚଐঢ়ଶͷ༹͕֩ӷશମʹੜ੒ͨ͠ͷͪɼঃʑʹͦΕΒ͕݁߹ͯ͠φϊཻࢠͱͯ͠੒௕͢ΔաఔΛ‫͍ͯݟ‬ΔՄೳੑ͕ਪଌ͞ΕΔɽͳ͓ɼࠓճɼSAXS ͷղੳͰ͸ͻ΋ঢ়ͷߏ଄͕‫ܗ‬੒͞ΕΔͱԾఆͯ͠ߦ͕ͬͨɼFig. 4ͷ SAXS ϓϩϑΟʔϧͷ‫ܗ‬ঢ়มԽ͔Βߟ͑ͯɼԾʹ࣮ࡍͷ Au ཻࢠͷ‫ܗ‬ঢ়͕ผͷϞϧϑΥϩδʔͰ͋ͬͨ
ͱͯ͠΋ Fig. 5 ͷ d ͷมԽ͸ఆੑతʹ͸ਖ਼͍͠ͱߟ

Fig. 5. Time-dependent diameter of particles (left͑Β͑Δɽaxis) and Invariant Q (right axis), assume that shapeof nano-particle is wire.

࠷‫ʹޙ‬ɼόΠΞϧϏϯʹ࢒༹ͬͨӷʹ͍ͭͯϏσΦࡱӨ݁Ռʹ͍ͭͯ‫͢ٴݴ‬ΔɽFig. 6 ʹϏσΦ͔ΒΩϟϓνϟʔͨ͠ը૾Λࣔͨ͠ɽ਺ࣈ͸ࠞ߹͔Βͷ࣌ؒΛ෼ͷ SAXS ϓϩϑΟʔϧʹ͍ͭͯ͸͏·ࣜ͘ (2) Ͱ͍ࣔͯ͠Δɽ͓Αͦ 30 ෼‫ޙ‬ఔ౓͔Β༹ӷͷ৭͕มԽϑΟοςΟϯάͰ͖͓ͯΒͣɼಘΒΕͨฏ‫ۉ‬௚‫ ܘ‬d ͷ࢝͠Ίɼ45 ෼ఔ౓ʹ͸ɼ΄΅ӷશମ͕ࠇ͘ม৭͠ɼφਫ਼౓͕௿͍ͱߟ͑ΒΕΔ͜ͱʹ஫ҙͯ͠ཉ͍͠ɽ
 ∞1Q=I(q)q 2 dq(3)2π 0ϊཻࢠ͕ੳग़ͨ͜͠ͱ͕ਪଌ͞ΕΔɽ͜ͷ৭ͷมԽ͕Fig. 2∼5 Λ‫ݟ‬Δͱɼ·ͣɼXAFS ͔ΒಘΒΕΔ Au‫ݩ‬ૉͷՁ਺มԽͱ SAXS ͔ΒಘΒΕΔφϊཻࢠ੒௕ͱͰ࣌ؒมԽ͕ҟͳΔ͜ͱ͕Θ͔ΔɽFig. 3ɼ5 ΑΓɼAu ‫ࢠݪ‬ͷؐ‫ݩ‬͸൓Ԡ։࢝௚‫͔ޙ‬Βਐߦ͢Δ͕ɼφϊཻࢠͷ‫ܗ‬੒͸͔ͳΓ Au ‫ࢠݪ‬ͷؐ‫͕ݩ‬ਐߦͨ͠‫ॳʹޙ‬Ίͯ։࢝͢Δ͜ͱ͕Θ͔Δɽ͞ΒʹɼFig. 5 ͷ d ͱ Q‫͜ى‬ΔλΠϛϯά͸ɼXAFS ͷՁ਺มԽ͕΄΅Ұఆ஋ʹམͪண͖ɼSAXS ͷࢄཚ͕‫؍‬ଌ͞Ε࢝ΊΔ࣌ࠁͱ͓ΑͦҰக͢ΔɽҎ্ͷࣄ͔Βɼ༹ӷͷ‫ͨݟ‬໨ͷมԽɼՁ਺มԽɼཻࢠੜ੒ΛରԠ෇͚Δ͜ͱ͕Ͱ͖ɼຊख๏͕໨త௨Γؐ‫ࢠཻͱݩ‬੒௕աఔΛಉ࣌ʹ‫͢࡯؍‬Δख๏ͱཱͯ֬͠͞Εͨͱͨ͠ɽࠓ‫ޙ‬ͷ՝୊ͷมԽΛ‫ͯݟ‬ΈΔͱɼd ͸Ұ౓ 15 nm ఔ౓·Ͱ૿Ճ͠ࠓճɼXAFS/SAXS ಉ࣌ଌఆख๏ͷཱ֬Λ໨తʹͨ‫ޙ‬ɼҰ౓ 8 nm ఔ౓·Ͱখ͘͞ͳͬͨ‫ޙ‬ɼ࠶ͼ૿Ճ࣮‫ݧ‬Λߦ͍ɼ਺े෼ఔ౓Ͱ‫͜ى‬Δཻࢠੜ੒աఔͷ‫࡯؍‬ʹస͍ͯ͡ΔɽҰํɼQ ʹ͍ͭͯ͸ಉ༷ʹ్தͰҰ౓͕ՄೳͰ͋Δ͜ͱΛ֬ೝͨ͠ɽҰํͰɼ‫ر‬ऍ༹ӷͷͨ‫ݮ‬গ͍ͯ͠Δ͕ɼͦͷ‫ݮ‬গͷఔ౓͸খ͍͞ɽInvariant

Ί XAFS ଌఆͷ‫͕౓ײ‬খ͘͞ɼͦΕ͕࣌ؒ෼ղೳͷΛ‫ٻ‬ΊΔࡍͷখ֯ଆͷੵ෼ൣғ͕ෆे෼Ͱ͋Δ͜ͱΛ཯଎ʹͳ͍ͬͯΔࣄ΍ɼ์ࣹޫϋον֎Ͱͷࣄલͷ‫ۉ‬ߟྀ͢Δͱ Invariant ʹ͍ͭͯ͸΄΅࣌ؒͱ‫ʹڞ‬୯ௐҰࠞ߹͕ඞཁͳ͜ͱ͔ΒɼՁ਺มԽͷॳ‫͔ظ‬Βͷଌఆ

Fig. 6. Time-dependent color of residue in a vial container (Numbers show time from mixing).

– 18 –ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू͸‫ݱ‬ঢ়Ͱ͖ͳ͍͜ͱ͕՝୊ͱͯ͠‫͛ڍ‬ΒΕΔɽ޻‫ۀ‬తँࣙͳԠ༻Λ೦಄ʹͨ͠৔߹ɼϓϩηε্ɼਝ଎ͳཻࢠ੒௕աఔ΍ࠞ߹λΠϛϯά͕՝୊ͱͳΔΑ͏ͳ‫͕ܥ‬ଘࡏ͢ΔɽࠓճͷଌఆͰɼφϊཻࢠੜ੒աఔΛ‫͢࡯؍‬Δͷʹద੾ͳख๏Ͱ͋Δ͜ͱ͕෼͔ͬͨͨΊɼࠓ‫ޙ‬͸ɼXAFS ‫౓ײ‬ΛߴΊΔํ๏΍์ࣹޫϋον಺Ͱͷ༹ӷࠞ߹ख๏Λ։ൃ͢Δ͜ͱ΋೦಄ʹख๏ͷ։ൃΛਐΊ͍ͨɽࠓճͷ‫ڀݚ‬Λߦ͏ʹ౰ͨΓɼฌ‫ཱݝݿ‬େֶ࢈ֶ࿈‫ܞ‬ɾ‫ڀݚ‬ਪਐ‫ޫࣹ์ߏػ‬φϊςΫηϯλʔͷ‫܂‬ຊ࣎ੜࢯɼ໺੉૜ࢢࢯɼཥཕࢯΛ͸͡Ίଟ͘ͷํʑʹ͓ੈ࿩ʹͳΓ·ͨ͠ɽ͜ͷ৔ΛआΓ͓ͯྱΛਃ͋͛͠·͢ɽࢀߟจ‫ݙ‬ࣄ‫΁ۀ‬ͷߩ‫ݙ‬ฐࣾͰ͸ɼ‫ܦ‬Ӧଟ֯Խʹ൐͍ɼ༷ʑͳ঎඼ΛऔΓѻ͍ͬͯΔɽࠓճղੳର৅ͱͨ͠ӷதͷཻࢠੜ੒աఔΛ༻͍Δ޻‫ۀ‬੡඼΋৮ഔɼృྉɼߏ଄վ࣭ࡎɼిࢠࡐྉ౳ଟ‫ʹذ‬ΘͨΔҝɼͦΕΒͷ੡඼։ൃΛՃ଎͢ΔͨΊɼੜ੒ϝΧχζϜͷఏ‫͖ͰݙߩͰܗ͏͍ͱڙ‬Δͱߟ
͍͑ͯΔɽ

– 19 –[1] খੴᚸ७ɼੴҪจ༝ஶɿʮφϊཻࢠͷ͸ͳ͠ʯॳ൛ୈ 1 ࡮ɼ೔‫৽ۀ޻ץ‬ฉࣾ (2006).
[2] J. Polte et al.: J. Am. Chem. Soc. 132, 12961301 (2010).
[3] X. Ji et al.: J. Am. Chem. Soc. 129, 1393913948 (2007).