電気化学者が挑んだ in situ XAFS 計測のあれこれ ³Ĺ ÀŐLjãêãêǘ×ŢŤÝŹêŵžǘ [email protected] 1ǨƎƩ ãêǘÃßăĸƱŻTǠ:c2ħò±įƬS·²dDeņ£U5LI_TT2Ɩ ƺTŵžOUR=2ŵžîTǮ9ĕ¤6ǯŭRďƥO5LII^2íǚSƖ¸Tŵž Sħò±iºŧDe@PiĎƴBITU2 ûSŦƍŵÕ§ǥ¸èĀŜĬǝō ŵžÛůy|SŴ¡B2Ÿ;ïDeŵž}TóĿŵžÐǦš ǧ;2 ţŵĥŶŵžĔS9>eƻ ! ƏÏÈū±¸±iŧ6NǝłŗŒũǟTŌiƲY b72PƩ6·BIIJ:cJLI3ÅŨŵžÐǦš Ľãǧ`ć÷ŵžÐǦţŵǧT ¼iĄN2āc;ǕūBIŗŒySǒ`ŬǒTǝł`ÆśǝłiƊƽ\2 ÙT¸±ǝŋ¿êyiŃƄBIT; ûT@PO5e3Gf Ǘ2¨ü:T íǤO2ǝ¥Ä½IJTũǟŌTƻ ! ƏÏÈū±xsTŕìSlBI;2 ʼnÒ¨c:Tà¿;ƦŕO<IS_::hcE2µšČTǥ6|TÉĄSUƗ cE2@TU¢ųşĐO5eǦšÖ2ŵžñƵià8IĭB6;Džô BN6eǧ3Į2 ûSĔõƊƐ;ĖƟŵžƊÍ .#($ SĦàAf2 wmsǮÕ§ǥ¸èĀŜĬǝōíŧ¿ĢDžĖƟǕūÛůĖƟǕū ǭǬǫļĬ TŃDŽǰÇĊǰŝƸź¾ƧľǯTň§PRLI@P;åņPRd2ŵž´ðS ! iƊ \ƽjJŵžiíįDeĉƣ;ťCI3G@O2ÀãƨyǦš ÀãƨçŹêŵž ĔǧTķ®ĨĠPǥƚŶĨĠSŲƳB2. Ƣŀǔ§S9>eǝłƨçÇĊiƿƹ DeI^T (* ,(-. ǝŋ¿ê ! SÉdƊ]@PSRLI3@@OU2ƭĬƲơ: cæ[d2&/ ,(-. ǀLJ ! ŕìiƋN2(* ,(-. ǝŋ¿ê ! ƪŕSƗe[OT LJŻiƿLNa<I63 2ǨCu2(Hdatrz)2 ƨçPǏƇNj°ÇĊ šşTÕ§ǥ¸èĀŜĬǝōǦǧSŧ6cfeǝłƨçPBNUSŬǒƆÍ ǒǦǧ;ƘŭJ;2ÚƛǑ`uxǟSÑǢiĘ8N6eI^2ë«:Mǥŏ ČRǞŬǒƆǏƇNj°ǝłƨçTǕū;ƾûŮjSƞhfN6e3ŞSp{ ǦſŋłǧS9>eǏƇNj°ÇĊǦǧU2 iƨçSŧ6N_ã<Rnr Ĥä;Ư^cfeZQdž=2bdǥŏČiĵDeƨçTǕū;Ķ[fN6e3Ɩ ŚũT ƨçPBN~pzǦ"$ǧ`vs $ Ǐ¿ǎƇǦ$ǧRQTǒõ ǎƇTÇĊĈ;ĵĶƤAfN9d2ŞS "$ TÇĊĈUǓâŀǔ§OŃđAfN 6e@P:c2ń4Rǔ§;ŁƫAfN<I3 ûTIJřOĴ_ŏČTǥ6ǓƆ ǝłƨçPBNǓŀǔ§Ô ;éÖB2GTǥ6ƨç ŏČSƷDeÇĊņŃiƧıDeI^S (*,(-.! ŕì iŰěBIŵžiǕæBI3ŞSĒ4;ǖĈiĚLIř U2 ǕæŇǙOU2ǏƇ¸è;ǪMT . loSŅ: >ŃDŽOÏŴB2G@SǝèǦPǧ;ǩMEMź ¾BNa<2ǁO ƌÍ;¹f2ĴƉŭSUŌPBN Ô 1.Ǔŀǔ§ Cu2[Hdatrz]2 TŃDŽ ƕǛBNa=LJŻi2(*,(-.! SbLNűġŕìO< eTOUR6:Pƒ8IP@gS5e3_Kgj2ÌŇǙ S9>eÇĊǃüiűġŕfe@P;ţčŭOU5e;29Gc=ğ8cfeÊƔ Č;5eTUĂǃŇǙPReLJŻTÅèǍƑT\O5d2@Tb7RƪŕU ƨç O_ĺJRAfNU6R63 Normalized abs. / a.u. 3Ǩex situ XAFS ŕì [ E 2 Ǔ Ƣ ŀ ǔ § T Ć ƌ ij 2.0 Ǧ.%"-+1ǧPp~sǦǧ 1.5 ę§SÎCǔ§ięĚBIƨçƅĻ Cu/KB catalyst Ǧ. $"-")0,-ǧiGfHfŧĎB2 1.0 ƅĻPœÍBN2ǀLJŧ~i©ơB I3ÆśŧƭĬPBNǓƃ2Ǐ¿Ǔ Cu(I) Cu O 0.5 Ǧ.2.ǧƅĻ`Ǔkǔ§iÎń CuO Cu(II) Cu (Hdatrz) S OúǐBN~SBI_T_ŧĎ 0.0 8960 8980 9000 9020 9040 9060 B2+(*' 9bW O Energy / eV ǀLJ ! ŕìiƞLI3ÌżƭĬT ! Ô ÌżƭĬT ! xs iÔ SŷD3ǔ§ƌijPƨçƅĻT ! xsU5[døŪ;R=2ĈǒõU .O5e@P; . 9bW . P ŊƼDe@POh:e3! оOU2ǔ§ƌijPƨçƅĻOUıc:Slj6;5 d2AcSƨçƅĻOUęĚǑSbLN ! о;à¿BNa=@P;h:LI3 ǔ§ƌij9bWƨçƅĻT ! оTnàģŎĀOU2. ` . áS2 .. Pƒ8cfe s;ƦŕAfI3@fcTŎĀU2¦ŔOTŕìO_ƦŕA fII^2îŔTŎĀƧľO_Á¸SǡO<e@P;h:LI3G@O2ċǣT (*,(-. ŕìSĜēDe@PPRLI3 4Ǩ(* situ ǝŋ¿ê XAFS ŕì ǝŋ¿êÇĊi ! OƿƹDeÜÍ2ǪMTÑǢř;5e3MUǝƧƸŗŒT éÖO5d2! Ə;ŗŒSbdĩAfNËþü;ý=Re@P;ĝ?cfe3_ 7MTÑǢU2ǝƧƸŗŒPġƨBN6eÜĔSB:ǝ¥;ĽO<R6@PO 5e3ƭĬ:cTËiĄeI^SU2ƭĬŘüiÞãAFfVƙ6TJ;2ƨç ƅĻiŽöBNĀđBIǝłTÜÍ2ƨçö´njSǝƧƸŌŗŒ;őǀBR>fV2 ǝ¥i¬ĚO<R63Ē4U2ǝłǝ¥iØƂSĽO<eƜ6ƨçöiNJėB2 ĉŚŭSƝ± ! ŕìO (* ,(-. ƦŕiDe@PPBI3@TIJ2ƨçi¬ĚDe ǝłGT_TiƁPB2ƁTƠ¯:c ! Əi²òƓǟÇòOĄcfeƝ± ! ƏiŁ ·De@PO2! Ə;ǝƧƸŌŗŒiǂLJ 2.0 De@PR=2! ŕì;ÊƔR¸±ǝŋ ¿êyiǕūBI3@T¸±ǝŋ¿êy 1.5 U2ǝƧƸŌŗŒiBR;cŕì O<eI^2ŗŒŖ^Oqxit 1.0 negative De@PO2ǜÓŋi»ąDe@P;O< 0.5 e3DRhK2ƀƇitDe@P OǝłÇĊ;DžƞBR6ŏČşĐi2Ǐ positive 0.0 ƇitDe@POǏƇNj°ÇĊDž 8960 8980 9000 9020 9040 9060 ƞIJT ! iŕìDe@P;O<e3Ô Energy / eV SUŏČǜÓŋOĄcfI ! x Ô . ǝłS9>e ! Tǝ¥ªéČ sTǝ¥ªéČiŷBN6e3ǝ¥i ƶSà¿AFeP2& ƾT s;ÞãBƢĪTƂÏÈř;Ư^cfe3 @fU .Ĉ; .XPNj°Af2GT đ¸TŊ;ǝ¥SbLN»ąO<e @PiŷBN6e3ƮƈSM6NUÿİưıDe3 ƃīŠ ǍùƷĬ(ppt)iÆśBN=JA63 2 Normalized abs. / a.u. 2 2 0.904 V vs. RHE (0.3 V vs. Ag/AgCl) at pH7 0.804 V (0.2 V) 0.704 V (0.1 V) 0.604 V (0.0 V) 0.504 V (-0.1 V) 0.404 V (-0.2 V) 0.304 V (-0.3 V) 0.204 V (-0.4 V) 0.104 V (-0.5 V)
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