B 0 5 0-5
双極子核 I=1/ 2 四極子核 I 1 e Li Be B C N F Ne Na Mg 黒字はNMR 観測不可 Al Si P S Cl Ar K Ca Sc Ti V Cr MnFe Co Ni Cu ZnGaGe As Se Br Kr RbSr Y Zr NbMoTc RuRhPdAgCd In Sn SbTe I Xe Cs Ba La f Ta W Res Ir Pt Au g Tl Pb Bi Po At Rn Fr Ra Ac Ku a La Ce Pr NdPmSmEuGdTbDyo Er TmYbLu Ac Th Pa U NpP uamcmbk Cf Es FmMdNo Lr Red Symbols = I=1/2 nucleus Blue bars = Natural abundance sensitivity range bars = 100% enrichment sensitivity 四極子核は魅力的 でも
NMR 超伝導磁石 試料 NMR 送受信機
CSA 300 200 100 0 300 200 100 0 200 100 0-100 600 400 200 0-200 -400
B 0 X 54.7 度試料 Z Y
10μs 10 ms -40 0 40-40 0 40 250 200 150 100 50 0 40 0-40 40 0-40 200 150 100 50 0 100 50 0-50 -100
双極子核 I=1/ 2 四極子核 I 1 e Li Be B C N F Ne Na Mg 黒字はNMR 観測不可 Al Si P S Cl Ar K Ca Sc Ti V Cr MnFe Co Ni Cu ZnGaGe As Se Br Kr RbSr Y Zr NbMoTc RuRhPdAgCd In Sn SbTe I Xe Cs Ba La f Ta W Res Ir Pt Au g Tl Pb Bi Po At Rn Fr Ra Ac Ku a La Ce Pr NdPmSmEuGdTbDyo Er TmYbLu Ac Th Pa U NpPuAmCmBk Cf Es FmMdNo Lr
2- B1 B2 B2 B1 B1 B2 10 B 11 B e 2 qq/h η (Mz) B1 1.042 0.711 B2 5.4 0.10 B1 0.487 0.714 B2 2.544 0.089 10B: Izv. Vyssh. Uchebn. Zaved. Fiz. 29, 3 (1986) 11B: J Chem. Phys., 38, 1912 (1963) 11 B B2 B1 11 B(I=3/2) 10 B * MAS 120 60 0-60 -120 * /ppm 20 0-20 Chemical shift / ppm
100 50 0-50 -100-150 -200
B1 B2 B2 B1 2- B1 B2 MAS 静止 * 120 60 0-60 -120 /ppm MQMAS や STMAS という二次元測定で 2 次の四極子相互作用による線形を 2 次元的に分離することも可能 30 20 10 0 10 MQMAS B2 B1 30 20 10 0 10 Chemical shift/ppm
δiso / ppm e 2 Qqh -1 / Mz η 30.4 3.5 0.4 18.8 2.7 0.2 0.94 < 0.1 0 40 20 0-20 Chemical Sift (ppm) 40 20 0-20 Chemical Sift (ppm)
hbn cbn calc. ref. 1 calc. ref. 2 e 2 Qq / h 2.85 2.936-0.72 < 0.05 (Mz) η 0 0 0.01 0 1) Solid State NMR 12, 1-7 (1998) 2) Solid State NMR 8, 109-121 (1997)
30.0 20.0 10.0 0 B- B site2 site1 site3 site2 30.0 20.0 10.0 0 Chemical shift / ppm M.Murakami et al., Solid State NMR, 2007 (31) 193.
0.000 (a) -0.005-0.010-0.015-0.020 FC ZFC Magnetization (emu/g) -0.025 0.000-0.005-0.010-0.015-0.020 0.000-0.005 (b) (c) -0.010-0.015-0.020 0 2 4 6 8 10 Temperature (K)
10 0 (a) dimension (ppm) (isotropic) F1 10 20 30 20 0 20 B1 B2 30 20 10 0 10 (b) 40 60 80 100 100 80 60 40 20 0 20 F2 (MAS) dimension (ppm)
(a) 1 11 B decouple recouple 90 o 90 o 90 o t 1 Δ t 2 (b) 11 B 90 o t 1 mixing t 2 90 o 90 o (c) 11 B t 1 t 2
(a) B2 B1 B2 B2 B1 B1 2- -40-20 0 F1 20 40 (b) 40 20 0-20 -40 F1 0 40 80 120 80 40 0 F2 120
(a) (b) (c) 150 100 50 0-50 -100 Chemical shift / ppm
1) Yazawa, T. Key Eng. Mater.1996, 15, 125 2) Yazawa, T. Porous Ceram. Mater. 1996, 115, 125-146. Na -B 2 2 Si 2 pore Si 2 anealing acid treatment 500~650 C borosilicate glass phase separated glass porous glass
29 Si Q3 Q4 11.7 T Experimental d c b -70-80 -90-100 -110-120 -130-140 -150 a 23 Na Na + (aq) Na (solvated) + 21.8 T Simulated 11.7 T 21.8 T 30 20 10 0-10 -20-30 -40-50 27 Al four-coordinated 21.8 T 25 20 15 10 5 0-5 -1025 20 15 10 5 0-5 -10 Chemical shift / ppm Chemical shift / ppm 90 80 70 60 50 40 30 20 11 B 30 20 10 0-1 Chemical shift / ppm 21.8 T
d b-d c 20 16 12 8 4 0-4 b d-b a -4 0 4 8 12 16 20 trigonal tetrahedral Si B (3, ring) B B (4, 4Si) Si B Si B B Si boroxol ring Si B (4, 3Si1B) trigonal/non-ring Si B B B B Si ring boron?? Si B (4, 2Si2B) B (3, non-ring) Si B B B B B B(3,borate) B B B B B B B(4,borate) B B