Зюбина Т.С, Зюбин А.С., Добровольский Ю.А., Волохов В.М
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Transcript of Зюбина Т.С, Зюбин А.С., Добровольский Ю.А., Волохов В.М
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: - . ., .., .., . - 2012
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: 2H2 + O2 => 2H2O : . : , : , .
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Ptn Ptn SnO2 SnO2 FSA- H2 1/2O2 H2OH+H+IIIIII
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- , , (DFT) (GGA=PBE) , 400 , , , VASP. PAW ( 4-8 288-144 ( (SnO2)96 - (SnO2)48 ).
: - 0.01-0.02A, 0.05-0.10 , - - 0.1-0.3
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11
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Ptn n-1/3 [V. Kumar, Y. Kawazoe , PHYSICAL REVIEW B , 2008, 77, 205418 ].
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Ptn SnO2 H2 H+H+I
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Pt6 Pt19 SnO2.SnO2(110)SnO2(001)
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Pt6 Pt19, SnO2
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C- H/Pt/SnO2
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I, SnO2(001)
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, SnO2 :
6(Sn) 3(O)
4(Sn) 2(O) - I, SnO2(001) 5,6(Sn) 2,3(O) - II, SnO2(110)
5(Sn) 2,3(O) - III, SnO2(100) 4,5(Sn) 2,3(O) - IV, SnO2(-1-11)
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I-IV SnO2 -
4(Sn) 2(O) 5,6(Sn) 2,3(O) 5(Sn) 2,3(O) 4,5(Sn) 2,3(O) I, SnO2(001) II, SnO2(110) III, SnO2(100) IV, SnO2(-1-11)
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SnO2(001)
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Ptn SnO2 1/2O2 H2OH+H+II
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Pt19,
- Pt19, p(1.2 - 1.7 )
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OH H2/Pt19/SnO2
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O-O 2 11
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O-O
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(8) (19).
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OH
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OH-. Z , =>
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FSA- H+H+III
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[2,4-FSA*2H2O]4 [(CH3)3C6H2SO3-*H5O2+]
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-2,4- 3+ (~2,5)
a = 5.959(1) = 71.08(1)0b = 7.995(1) V = 541.30(8) 3c = 12.025(1) Z = 2 = 88.71(1)0.. P(-1) = 87.23(1)0R1 = 0.0309
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:
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C -- PVA/FSA = 16/1 75% PVA/FSA = 8/1 32%.
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/ / Nafion
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PVA .
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FSA*nH2O , n=14.
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. c .
(110)R3, -50% O
(100)R1, -50% O
De(O2) 3.86
De(O2) 3.04
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Pt(100) ~ 0.4 . ~ 0.2 .
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2 Pt79. Pt79 (111) ~ 1.1
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: Pt6 H2 [67 ] Pt4H Pt-HDFT/ B3LYP/MWB,aug-cc-pVTZ) [63]
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:a) , b) c)