ポテンショスタット potentiostat - bas.co.jp

1 1 1.. ; source ; sink HOMO LUMO HOMO LUMO 3 . 3 Cdl Rct Rs LUMOHOMOe LUMOHOMOeO + e RRO + e LUMOHOMOe LUMOHOMOe LUMOHOMOe LUMOHOMOeO + e RRO + e LUMOHOMOe LUMOHOMOeO + e RRO + e LUMOHOMOe LUMOHOMOe LUMOHOMOe LUMOHOMOeO + e RRO + e WCRpotentiostat WCRpotentiostat 2 Cdl Q=CdlE dE/dt Cdl i=dQ/dt= CdldE/dt

2 3 1 2 3 3 2 1 Zi Zf 1 . 2.

3 + + + + + + + + CdlRctRsCdlRctRs 3 . ininfoutVRRV = infoutiRV = H inoutVRRV +=121 R1 R2 1 Vout=Vin .. + + + +CWRefOp-1Op-2iCell + + + + + +CWRefOp-1Op-2iCell 4 1 ei Op-1 ei 1 2 Op-2 2 2 Op-1 3 3 HPLC 10

4 10 . + + + +CWRe fOp-1Op-2i + + + + + +CW1Re fi1 + + + + + + + + +RRE1 + + + + + + + RRRE2W2 E = E2 E1i2W1W2 RefE1 E1E2E1E2 E + + + +CWRe fOp-1Op-2i + + + + + +CW1Re fi1 + + + + + + + + +RRE1 + + + + + + + RRRE2W2 E = E2 E1i2 + + + + + +CWRe fOp-1Op-2i + + + + + +CW1Re fi1 + + + + + + + + +RRE1 + + + + + + + RRRE2W2 E = E2 E1i2W1W2 RefE1 E1E2E1E2 E 5 11 1M H2SO4 40 V

5 H2 2H+ + 2e Ag + Cl AgCl + e KCl 12 aCl sat KClaqAgAgClfritsat KClaqAgAgClfrit 6 KCl vs NHE Ag Hg SCE KCl vs NHE 13.

6 IR 14 RsRuCERefWE i iRu CdlRctRsRuCERefWE i iRu CdlRct =ClaFRTEEln0 7 CV 100 200 500 CV 15 14 Rct Cdl 50 V E ( ) 0 i(0) Ru 0 E 16 Ru Ru iR iR OK 1 A + e B Ru 1; 0 2; 100 3; 200 4; 500 100mV/s1 A + e B Ru 1; 0 2; 100 3; 200 4.

7 500 100mV/s() =dluuCRtREtiexp E/Rui E V E/Rui E V 8 100 16 iR Rpf Eset fiRu Ru 16 iR f op1 Ru Eset Rpf f PC iR . JP JP M KC M HC K+ H+ H+ K+ H+ 1.

8 H+ JP EsetRRRRfRpffop1op2op3 CRefWEo=iRfEsetRRRRfRpffop1op2op3 CRefWEo=iRfH+ OH-198K+ + + ClO4-68NH4+ 9 JP KCl 17 17. KCl JP KCl t t 25 C V a1 a2 1M 3M V, 10 V KCl JP NaCl V V . q1 q2 0 Bu4N ClO4 BF4 PF6 ()

9 21lnaaFRTttEJP + = = a1 KCla2 KClK+Cl- a1 KCla2 KClK+Cl-20214rqqf = 10 THF 1 18 M CV THF [Bu4N][A] A TFAB PF6 TFAB B(C6F5) 5V/s GC iR (85 ) 18 M THF CV V/s CV Bu4 NPF6 iR iR THF CV B(C6F5) 19 ( ) ( 2 ) CV Bu4 NPF6 Bu4N B(C6F5) PF6 19 M ( ) CV Bu4 NPF6 Bu4N B(C6F5) Ф Pt 1) Geiger et al.

10 , Anal. Chem., 76 , 6395 (2004) 2) Geiger et al., Angew. Chem. Int. Ed., 38 , 248 (2000)