FUNCIONARIOS DEL MINISTERIO COORDINADOR DE LOS SECTORES ESTRATÉGICOS
6.3 Combinación de Habilidades por Variables TABLA No.27
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Appendix A
Supplemental Data for Ch. 3: Characterizations of Cu-Ligand Interactions
Figure A.1. Single electrode polarization curves of the experiments using four Cu electrodes: CuNP, CuNP-DAT, CuNP-PZ and CuNP-TRZ.
Figure A.2. SEM images for CuNP, CuNP-DAT, CuNP-PZ and CuNP-TRZ electrodes before and after flow cell testing.
Figure A.3. In situ SER spectra of the Cu electrode surface during cathodic polarization in the absence of CO2 for regions of (a) low, (b) middle, and (c) high Raman shift values. The
electrolyte was Ar-purged 1 M KOH + sat’d Ca(OH)2 + 10 mM DAT + HClO4 (to adjust pH ≈
7.8). 0.5 V -1.0 V 700 900 1100 1300 Intensity Raman Shift (cm-1) 300 400 500 600 Intensity Raman Shift (cm-1) 1400 1500 1600 1700 Intensity Raman Shift (cm-1) a b d g i k (b) (a) 0.5 V -1.0 V 0.5 V -1.0 V c f e j h k l n o (c) m
Table A.1. Raman mode assignments. ν = stretch, δ = in-plane deformation, γ = out-of-plane deformation τ = torsion, ρ = rock, ω = wag.
Peak Raman Shift (cm-1) Mode Assignment References DAT ClO4- a 349 δ(C-NH2) + τ(NH2) 65 b 376 δ(C-NH2) + τ(NH2) 65 c 489 γ(C-NH2) 65 d 531 δ(C-NH2) 65 e 662 ω(NH2) 65 f 811 δ(ring) 65 g 934 ν(ClO4-) 66 h 1043 ν(ring) + δ(ring) 65, 67, 68 i 1135 ρ(NH2) + ν(ring) 65 j 1388 δ(N-H) 65 k 1415 ν(ring) 65, 68 l 1494 ν(ring) + ν(C-NH2) 65, 67, 68 m 1557 ν(ring) + ν(C-NH2) 65, 68 n 1614 δ(NH2) 37, 65, 68 o 1645 δ(NH2) 65, 68
Figure A.4. Normal ex situ and surface-enhanced in situ Raman spectra of DAT metal complexes (black, red, and blue lines) and free DAT (pink, green, and navy).
Figure A.5: In situ SER spectra of CO2 reduction at the Cu electrode surface during cathodic
polarization in the region of ethoxy vibrations. The electrolyte was 1 M KHCO3 + sat’d
Ca(OH)2.
250
450
650
850
1050 1250 1450
Neat AgDAT Solid
Cu Surface @ 0.5 V w/Ar + DAT Cu Surface @ 0.5 V w/CO2 + DAT
Neat DAT Solid
Cu Surface @ -1 V w/Ar + DAT Cu Surface @ -1 V w/CO2 + DAT
Intensity
Raman Shift (cm
-1)
700 900 1100 1300 Intensity Raman Shift (cm-1) 18 19 0.5 V -1.0 VAppendix B
Supplemental Data for Ch. 5: Full List of Raman Mode Assignments
Table B.1. Raman mode assignments. ν = stretch, δ = bend, τ = torsion, ρ = rock, ω = wag.
Peak Raman Shift (cm-1) Mode Assignment References SES SPS SBS SES + Cl- SPS + Cl- SBS + Cl- a 290 289 294 ν(Cu-SO4) 66-72 b 287 280 277 ν(Cu-Cl) 36, 39, 67-70, 73 c 371 undefined τ-mode 64 d 435 441 439 441 δ(CCC/CCS) 59, 60, 62 e 527 529 530 528 531 535 ρ(SO2) 54, 64 f 570 569 571 566 δ(SO2) 64 g 616 617 609 612 620 609 gauche ν(C-S)thiol 53, 58, 60, 61, 63 h 632 631 gauche ν(C-S)thiol 39, 53, 54, 57-61, 63 i 683 677 680 693 681 679 trans ν(C-S)thiol 39,57-61 j 725 733 726 733 726 ρ(CH2) 39, 53, 54, 59, 63 k 787 794 790 794 796 791 ν(C-SO3) 39, 55, 57 l 849 851 ρ(CH2) 39, 60 m 907 916 900 917 ρ(CH2) 59, 62 n 957 952 gauche ν(C-C) 60 o 970 968 972 969 ν(SO4 2- ) 39, 53, 68, 70-73 p 1023 1024 1026 1034 1033 1026 trans ν(C-C) 59, 61 q 1210 1206 1200 ν(SO2) 39, 54, 55, 72, 74, 75 r 1240 1231 1248 1240 1248 ω(CH2) 39, 54, 55, 62, 63 s 1288 1271 1304 1294 1271 1303 ω(CH2) 39, 56, 60, 62, 64, 65 t 1345 1353 1345 1347 δ(CH2) 39, 62, 65 u 1404 1417 1418 1407 1416 1413 δ(CH2) 39, 54, 56, 62