XAFS ࡜ DV-Xǂ ศᏊ㌶㐨ィ⟬࡟ࡼࡿ◪㓟Ỉ⁐ᾮ୰ࡢỈ࿴ࢫ࢝ࣥࢪ࣒࢘࢖࢜ࣥࡢᵓ㐀‫ۑ‬ẚ჆㣁ኴ㸯ࠊྜྷ⏣ாḟ㸯ࠊᰩᓮ ᩄ㸯ࠊ㝮㇂࿴Ⴙ㸰ࠊᒣཱྀᩄ⏨㸯㸯⚟ᒸ኱⌮ࠊ 㸰బ㈡ LSỈ⁐ᾮ୰ࡢࢫ࢝ࣥࢪ࣒࢘(III)࢖࢜ࣥࡢ㓄఩ᩘࡣࠊ✀ࠎࡢ᪉ἲ࡟ࡼࡾ㸴㹼㸶ࡢ್ࡀሗ࿌ࡉࢀ࡚࠾ࡾࠊ⤫୍ⓗ⤖ㄽࡣᚓࡽࢀ࡚࠸࡞࠸ࠋᡃࠎࡣࠊ◪㓟ࢫ࢝ࣥࢪ࣒࢘Ỉ⁐ᾮࡢ X ⥺ᅇᢡᐃ࡜ Empirical Potential Structure Refinement (EPSR) ࣔࢹࣜࣥࢢ࡟ࡼࡾࠊࢫ࢝ࣥࢪ࣒࢘࢖࢜ࣥࡢ㓄఩ᩘࢆ㸵࡜Ỵᐃࡋࡓࠋᮏ◊✲࡛ࡣࠊ◪㓟ࢫ࢝ࣥࢪ࣒࢘Ỉ⁐ᾮࡢ Sc K XAFSᐃ࡜DV-XĮ ศᏊ㌶㐨ィ⟬࡟ࡼࡾࠊࢫ࢝ࣥࢪ࣒࢘࢖࢜ࣥࡢ㓄఩ᩘ࡜㓄఩ᵓ㐀ࢆ᫂ࡽ࠿࡟ࡋࡓࡢ࡛
ሗ࿌ࡍࡿࠋ
 1 mol/L ◪㓟ࢫ࢝ࣥࢪ࣒࢘Ỉ⁐ᾮࡣࠊᕷ㈍ࡢ≉⣭ヨ⸆ࢆᑡ㔞ࡢ◪㓟ࢆຍ࠼ࡓ⵨␃Ỉ࡟⁐ゎࡉࡏ࡚ㄪ〇ࡋࡓࠋSc K XAFS ࢫ࣌ࢡࢺࣝࡣࠊబ㈡┴❧஑ᕞࢩࣥࢡࣟࢺࣟࣥග◊✲ࢭࣥࢱ࣮ࡢ BL15 ࡟࠾࠸࡚ᐊ࡛

ᐃࡋࡓࠋࡲࡓࠊDV-XĮ ࡢィ⟬࡟ࡣࠊ6~9 㓄఩ࡢ⤖ᬗᵓ㐀ࢹ࣮ࢱ࡜ EPSR ࣔࢹࣜࣥࢢ࡟ࡼࡿ⁐ᾮᵓ㐀ࢹ࣮ࢱࢆ⏝࠸ࡓࠋ XAFS ࢫ࣌ࢡࢺࣝ࡜ DV-XĮ ࡟ࡼࡿࢫ࣌ࢡࢺࣝࡢẚ㍑࠿ࡽࠊ6, 8, ࠾ࡼࡧ 9 㓄఩ࡢ⤖ᬗᵓ㐀ࡣᐇ್ࢫ࣌ࢡࢺࣝࢆ෌⌧ࡋ࡞࠿ࡗࡓࠋ୍᪉ࠊEPSR ࣔࢹࣜࣥࢢ࠿ࡽᚓࡽࢀࡓ⁐ᾮᵓ㐀ࢹ࣮ࢱ࡛࠶ࡿ 7 㓄఩ࡣࠊࣉࣞࣆ࣮ࢡ࡜ XAFS ࢫ࣌ࢡࢺࣝࡢ࠸ࡎࢀࡶᐇ㦂್࡜ࡼ࠸୍⮴ࢆ♧ࡋࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ◪㓟ࢫ࢝ࣥࢪ࣒࢘Ỉ⁐ᾮ୰ࡢࢫ࢝ࣥࢪ࣒࢘(III)࢖࢜ࣥࡢ㓄఩ᩘࡣ 7 ࡛
࠶ࡾࠊ6 ಶࡢỈศᏊ࡜ 1 ಶࡢ◪㓟࢖࢜ࣥࡢ㓟⣲ཎᏊ࠿ࡽ࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋXAFS䛸DV-XĮศᏊ㌶㐨ィ⟬䛻䜘䜛◪㓟Ỉ⁐ᾮ୰䛾Ỉ࿴䝇䜹䞁䝆䜴䝮䜲䜸䞁䛾ᵓ㐀䠄䠍⚟ᒸ኱⌮䚸䠎బ㈡LS䠅ẚ჆㣁ኴ䠍䚸ྜྷ⏣ாḟ䠍䚸ᰩᓮ ᩄ䠍䚸㝮㇂࿴Ⴙ䠎䚸ᒣཱྀᩄ⏨䠍⫼ᬒ,◊✲┠ⓗỈ⁐ᾮ୰ࡢࢫ࢝ࣥࢪ࣒࢘(III)࢖࢜ࣥࡢ㓄఩ᩘࡣࠊ✀ࠎࡢ᪉ἲ࡟ࡼࡾ㸴㹼㸶ࡢ್ࡀሗ࿌ࡉࢀ࡚࠾ࡾࠊ⤫୍ⓗ⤖ㄽࡣᚓࡽࢀ࡚࠸࡞࠸ࠋᡃࠎࡣࠊ◪㓟ࢫ࢝ࣥࢪ࣒࢘Ỉ⁐ᾮࡢX⥺ᅇᢡ ᐃ࡜Empirical Potential Structure Refinement (EPSR) ࣔࢹࣜࣥࢢ࡟ࡼࡾࠊࢫ࢝ࣥࢪ࣒࢘࢖࢜ࣥࡢ㓄఩ᩘࢆ㸵࡜Ỵᐃࡋࡓࠋᮏ◊✲࡛ࡣࠊ◪㓟ࢫ࢝ࣥࢪ࣒࢘Ỉ⁐ᾮࡢSc K
XAFS ᐃ࡜DV-XĮศᏊ㌶㐨ィ⟬࡟ࡼࡾࠊࢫ࢝ࣥࢪ࣒࢘࢖࢜ࣥࡢ㓄఩ᩘ࡜㓄఩ᵓ㐀ࢆ᫂ࡽ࠿࡟ࡋࡓࡢ࡛ሗ࿌ࡍࡿࠋ

Monte Carlo ィ⟬
Sc-Ow15U
J

001U

F(Q)

୕ḟඖᵓ㐀
23ύ

-0.56U DE12஧యศᕸ㛵ᩘ§ § g r ··U DE  kT ¨¨ ln¨¨ DDE¸¸ ¸¸© © g DE r ¹ ¹2. DV-XĮἲ䛻䜘䜛ศᏊ㌶㐨ィ⟬N0U DE | U DEධຊ䝕䞊䝍∝Ў‫܇‬ನᡯ∝∃⇬∙⇝∉∑∝ૠ݅ࡇ∝∈∑Ўྙ䡡ศᏊ㌶㐨

25٦ 0.1 MPa(Sc-O W)

Sc3+03. 㟁Ꮚศᕸゎᯒ

0.20.1

DgDE r | gDE
r004. 䝉䝹䝣䝁䞁䝅䝇䝔䞁䝖䠛䡡Ᏻᐃ?

510Coordination number㓄఩ᩘศᕸYes

4480 4490 4500 4510 4520 4530 4540
EnergyXAFSDV-XĮ䛻౑⏝䛧䛯ᗙᶆ䝕䞊䝍㓄఩ᩘ 6,8,9

EXANES

XANES

0.962 M Sc(NO3)3 aq
2.95 M
HNO3 aq

CN: 6(H2O) ṇඵ㠃య
CN: 8(H2O) bicapped trigonal prism
CN: 9(H2O) tricapped trigonal prism

2μt / a. u.

0Difference RDF⤖ᬗ䝕䞊䝍 CN6 CCDC 602519 , CN 8,9 CCDC 280508

㓄఩ᩘ 7

504682.8 Å4480 4490 4500 4510 4520 4530 4540

10r/Å4.25 ύEPSR modeling
Pair correlation functions(Sc-OW ,Sc-ON)
30

CN:9

CN:8

10

CN: 6(H2O)+1(ONO2) monocapped trigonal prism
CN: 7(H2O) monocapped trigonal prism
222
Intensity /a. u.

Sc3+EnergyCN:6H2O

Intensity /a. u.

22.15 Å4490

4500
Energy1045104490

4500
Energy1045104490

4500
Energy4510

2.13 ύg(r)Sc-O W

Sc3++ 13.0

10

CN:6+1Sc-O N

24r/Å68NO3-

Mean CN
0.4

0.4

Sc-OW

Sc-ONPopulation

0.3
0.2
0.1

0.3
0.2

468Coordination number

Sc-OW 6.2 㼼 1.0( rmax = 2.88 Å )Sc-ON 1.2 㼼 1.0( rmax = 2.79 Å )

1000

CN =

24
68Coordination number

2100.1
2

CN:72- 3.0
10

Intensity /a. u.

0Intensity /a. u.

20000

N 1s,2s,2p,3s,3d- 1.0
ON 1s,2s,2p,3s,3d

XAFS and DV-XĮ

X-ray measurements

0+3ィ⟬⤊஢⤖ᯝ䛸ウㄽ0㟁ⲴOW 1s,2s,2p,3s,3dH
1s,2s,2p

䡡㌶㐨䛻㟁Ꮚ䜢⨨䛟

No㌶㐨᮲௳
1s,2s,2p,3s,3p,3d,4s,4p

Intensity /a. u.

105Population

N

68-1Q/Å4ᐇ㦂⿦⨨䡡ཎᏊ㌶㐨

0.3

Experimental
EPSR

బ㈡䝅䞁䜽䝻䝖䝻䞁 BL15Sc K ( E = 4.5 keV)㏱㐣ἲ
1 mol/L ◪㓟䝇䜹䞁䝆䜴䝮Ỉ⁐ᾮ

1. ᩘ್ཎᏊᇶᗏ㛵ᩘ䜢ồ䜑䜛

53 2 -1

86DV–XĮ ศᏊ㌶㐨ἲ

100(D(r)-4Sr U0)/10 el Å?

Y3+ (0.90)௨๓䛾◊✲ 㓄఩ᩘ (CN)⤖ྜ㛗( ύ )3.9 – 5.1
NMR
6FT-IR7Raman
7
2.18
XRD
72.14 㽢 6, 2.47 㽢1
QM/MM
6+1+1
EXAFS
2.17㽢6, 2.32㽢1, 2.5㽢1μt / a. u.

᬴ܱ⇭∞⇥(ನᡯ᧙ૠ )Population

Sc3+ (0.75)౑⏝䛧䛯䝡䞊䝮䝷䜲䞁ᐃ䛧䛯྾཰➃ᐃ᪉ἲᐃ䛧䛯ヨᩱ

Empirical Potential Structure Refinement (EPSR)

4CNXAFSᐇ㦂

2(ri / Å)
Al3+ (0.54)

4490

4500
Energy4510: 䝇䜹䞁䝆䜴䝮䜲䜸䞁: 㓟⣲ཎᏊ

1: Ỉ⣲ཎᏊ
04490

4500
Energy: ❅⣲ཎᏊ

4510:㑄⛣☜⋡107.4 㼼 1.4
᭱䜒ᐇ㦂್䜢෌⌧⤖ㄽ
X⥺䚸EPSR䚸XAFS䚸DV-XĮἲ䜢⤌䜏ྜ䜟䛫䛯⤖ᯝ௨ୗ䛾䛣䛸䜢⤖ㄽ௜䛡䜛䚹X⥺䚸EPSR䛛䜙◪㓟䝇䜹䞁䝆䜴䝮Ỉ⁐ᾮ୰䛾䝇䜹䞁䝆䜴䝮䜲䜸䞁䛿䚸ỈศᏊ䛾㓟⣲ཎᏊ6ಶ䛸◪㓟䜲䜸䞁䛾㓟⣲ཎᏊ1ಶ䛷㓄఩ᵓ㐀䜢ᙧᡂ䛧䛶䛔䜛䚹

Sc-O distance1 : 2.132 Å
2 : 2.262 Å
3 : 2.019 Å
4 : 2.060 Å
5 : 2.153 Å
6 : 2.139 Å
7 : 2.169 Å

ᖹᆒ 2.133 Å
7
3
1

5

XAFS䚸DV-XĮ䛛䜙4◪㓟䝇䜹䞁䝆䜴䝮Ỉ⁐ᾮ୰䛾䝇䜹䞁䝆䜴䝮䜲䜸䞁䛿䚸distorted monocapped trigonal prism ᵓ㐀䜢ᙧᡂ䛧䛶䛔䜛䚹62