2.2 Ni
5.3.1 Pt Ni/LSAO
Ni/LSAO Ni/LAO Ni/ -Al2O3
24,25) Ni/LSAO
Ni (Ni0)
Ni/LSAO Pt
Pt 0.85 wt% Ni 1/20 Pt/Ni/LSAO
Ni/LSAO
37 Pt NiO Ni0
Ni Ni2+ Ni0 Pt
Ni Pt/LSAO
Ni/LSAO Fig. 1
Pt/Ni/LSAO
37) Pt Ni
(
) Pt Ni Pt Ni
Pt/Ni/LSAO Ni/Pt/LSAO Pt-Ni/LSAO (
) Fig. 2
(Pt/Ni; 52.7 % Ni/Pt; 48.1 % Pt-Ni; 46.5 %) 3 h (Pt/Ni; 39.2 % Ni/Pt; 38.2 % Pt-Ni; 36.2 %)
Ni/LSAO Pt/Ni/LSAO C1 (CO CH4 CO2)
Table 1 3 h
C1 C1 Pt : 17.0;
Ni/LSAO 3.0; Pt/Ni/LSAO ( ) 2.4; Pt/Ni/LSAO ( ) Pt Ni
Table 2 Ni/Pt/LSAO
: 2.4; Pt/Ni/LSAO 22.0; Ni/Pt/LSAO 3.2; Pt-Ni/LSAO 38)
Ni LSAO Ni/Pt/LSAO
Ni LSAO
111 5.3.2
Pt/Ni/LSAO Ni
XPS XANES H2-TPR
Pt/Ni/LSAO Ni Pt Ni 2p1/2 Pt4d5/2
XPS 37 C 1s (284.8 eV)
Ni/LSAO ( ) Pt/Ni/LSAO ( ) Ni/LSAO ( ) Ni 2p1/2
Ni/LSAO ( ) 876.78 eV Pt/Ni/LSAO
( ) 873.02 eV Pt Ni 2p1/2
Pt/Ni/LSAO ( ) Ni 2p1/2 Ni/LSAO ( )
873.90 eV Pt Ni
Pt/LSAO ( ) Pt/Ni/LSAO ( ) Pt/LSAO ( ) Pt 4d5/2
Pt/LSAO ( ) 315.92 eV Pt/Ni/LSAO ( )
316.53 eV Pt/LSAO ( ) 315.14 eV Pt Ni Pt4d5/2
Pt
Pt/Ni/LSAO Pt Ni Ni
Ni/Pt/LSAO Pt-Ni/LSAO ( )
Pt/Ni/LSAO 2
XPS Ni 2 Ni 2p1/2 Fig. 3
Ni 2p1/2 Ni/Pt/LSAO ( ) 873.17 eV Pt-Ni/LSAO (
) 873.10 eV Pt/Ni/LSAO ( ) Ni/LSAO ( )
Pt Ni Pt Ni Pt Ni
Pt/Ni/LSAO Pt Ni XANES
Fig. 4 Pt/Ni/LSAO ( ) Pt/LSAO ( ) Pt L -edge XANES Pt/Ni/LSAO
Pt/LSAO XPS Pt Ni
Pt/Ni/LSAO Ni K-edge
XANES 37
XPS (Ni ) XPS
XANES
Ni Ni0:NiO = 74.1:25.9
Ni Ni0:NiO = 26.3:73.7 H2
Pt Ni Ni Pt/Ni/LSAO
112
Ni
H2-TPR Ni/LSAO Pt/Ni/LSAO Ni/Pt/LSAO Ni
H2-TPR Fig. 5 Ni/LSAO 700 K 1000 K
Ni LSAO
Ni/LSAO
Ni/LSAO 1073 K 873 K
Pt/Ni/LSAO 620 K 700 K
Pt Ni
Pt/Ni/LSAO Ni (C7H8 CO H2)
Ni/Pt/LSAO ( ) 620 K 700 K 950 K
Pt/Ni/LSAO 620 K Ni/LSAO
1000 K H2 620 K H2
600 K Ni
5.3.3
Pt/Ni/LSAO Ni/LSAO
EXAFS STEM-EDX XPS Pt/Ni/LSAO
Pt Ni Pt/Ni/LSAO EXAFS
Pt/Ni/LSAO ( ) Pt L
-edge 37 Table 3 Pt-Pt
Pt foil Pt-O Na2Pt(OH)6
Pt-O
Pt-O Pt-Pt Pt
Pt-Pt 2.66 Å Pt foil
2.77 Å Pt/Ni/LSAO Pt Pt foil
Pt-Ni
2.56 Å 2.53 Å Ni-Ni 2.49 Å
Pt Ni Pt-Ni
Ni Pt
Pt-Pt Pt-Ni Pt/Ni/LSAO Pt Ni
(Pt/Ni 0.05) 39) Pt-Pt Pt-Ni
0.52 (Pt-Pt:4.12 Pt-Ni:7.88) 2.2 (Pt-Pt:8.08
113
Pt-Ni:3.68) Pt Ni
Ni Pt
Pt Ni
Pt/Ni
40-42) Pt Ni
Ni K-edge Ni Pt Pt-Ni
Pt/Ni/LSAO EXAFS Pt-Ni
STEM-EDX Pt/Ni/LSAO
37 Pt EDX Pt
Pt Ni
Pt Ni
STEM Pt/Ni/LSAO Ni/Pt/LSAO Pt-Ni/LSAO
Ni/LSAO Fig. 6
Ni/LSAO Ni 12.8 nm Pt/Ni/LSAO
3.2 nm Ni/Pt/LSAO 5.4 nm Pt-Ni/LSAO 5.6 nm Pt
22
Pt/Ni/LSAO Pt-Ni/LSAO
Ni/Pt/LSAO Ni/LSAO
Ni/LSAO (Ni/Pt/LSAO: 69 mg g-cat-1
Ni/LSAO: 57 mg g-cat-1)
Pt Pt/Ni/LSAO
Ni/Pt/LSAO XPS
873 K 0.5 h
Table 4 Pt/Ni/LSAO Pt/Ni 0.078 Ni/Pt/LSAO 0.044
(Pt + Ni)/Al 0.515 0.525
Pt Ni
Pt Ni
Ni LSAO
114
5.4
Ni/LSAO Pt
Pt Ni Pt/LSAO Ni/LSAO
Pt/Ni/LSAO Pt Ni
XPS PtNi Ni Ni/LSAO
Pt/Ni/LSAO Pt
Pt/LSAO Ni Pt
Ni Pt/Ni/LSAO
Ni H2-TPR
Pt Ni
EXAFS STEM-EDX Pt/Ni/LSAO
Pt Ni XPS Pt Ni
Pt/Ni/LSAO Pt/Ni Ni/Pt/LSAO Pt/Ni/LSAO
Pt Pt Ni
Ni LSAO Pt/Ni/LSAO
115
1) A.V. Bridgwater, Appl. Catal. A: Gen. 116 (1994) 5 47.
2) D. Sutton, B. Kelleher, J.R.H. Ross, Fuel Process. Technol. 73 (2001) 155 173.
3) Z. Abu El-Rub, E.A. Bramer, G. Brem, Ind. Eng. Chem. Res. 43 (2004) 6911 6919.
4) G.W. Huber, S. Iborra, A. Corma, Chem. Rev. 106 (2006) 4044 4098.
5) K. Polychronopoulou, J.L.G Fierro, A.M. Efstathiou, J. Catal. 228 (2004) 417 432.
6) K. Poluchronopoulou, C.N. Costa, A.M. Efstathiou, Appl. Catal. A: Gen. 272 (2004) 37 52.
7) K. Polychronopoulou, C.N. Costa, A.M. Efstathiou, Catal. Today 112 (2006) 86 93.
8) K. Polychronopoulou, A.M. Efstathiou, Catal. Today 116 (2006) 341 347.
9) R. Coll, J. Salvado, X. Farriol, D. Montane, Fuel Process, Technol. 74 (2001) 19 31.
10) H.J. Park, S.H. Park, J.M. Sohn, J. Park, J.-K.Jeon, S.-S. Kim, Y.-K. Park, Biores.
Technol. 101 (2010) S101 S103.
11) R. Zhang, Y. Wang, R.C. Brown, Energy Convers. Manage. 48 (2007) 68 77.
12) J. Srinakruang, K. Sato, T. Vitidsant, K. Fujimoto, Catal. Commun. 6 (2005) 437 440.
13) D. Swierczynski, S. Libs, C. Courson, A. Kiennemann, Appl. Catal. B: Environ. 74 (2007) 211 222.
14) C.Li, D. Hirabayashi, K. Suzuki, Appl. Catal. B: Environ. 88 (2009) 351 360.
15) C. Li, D. Hirabayashi, K. Suzuki, Fuel Process. Technol. 90 (2009) 790 796.
16) D.N. Bangala, N. Abatzoglou, E. Chornet, AIChEJ. 44 (1998) 927 936.
17) T.J. Wang, J. Chang, C.Z. Wu, Y. Fu, Y. Chen, Biomass Bioenergy 28 (2005) 508 514.
18) T. Furusawa, A. Tsutsumi, Appl. Catal. A: Gen. 278 (2005) 195 205.
19) M. Virginie, C. Courson, D. Niznansky, N. Chaoui, A. Kiennenmann, Appl. Catal. B:
Environ. 101 (2010) 90 100.
20) K. Poluchronopoulou, A. Bakandritsos, V. Tzitzios, J.L.G Fierro, A.M. Efstathiou, J.
Catal. 241 (2006) 132 148.
21) D.L. Trimm, Catal. Today 37 (1997) 233 238.
22) D.L. Trimm, Catal. Today 49 (1999) 3 10.
23) K. Urasaki, Y. Sekine, S. Kawabe, E. Kikuchi, M. Matsukata, Appl. Catal. A: Gen. 286 (2005) 23 29.
24) Y. Sekine, D. Mukai, Y. Murai, S. Tochiya, Y. Izutsu, K. Sekiguchi, N. Hosomura, H.
Arai, E. Kikuchi, Y. Sugiura, Appl. Catal. A: Gen. 451 (2013) 160 167.
25) D. Mukai, S. Tochiya, Y. Murai, M. Imori, T. Hashimoto, Y. Sugiura, Y. Sekine, Appl.
Catal. A: Gen. 453 (2013) 60 70.
116
26) Y. Sugiura, D. Mukai, Y. Murai, S. Tochiya, Y. Sekine, Int. J. Hydrogen Energy 38 (2013) 7822 7829.
27) D. Li, Y. Nakagawa, K. Tomishige, Appl. Catal. A: Gen. 408 (2011) 1 24.
28) K. Tomishige, S. Kanazawa, M. Sato, K. Ikushima, K. Kunimori, Catal. Lett. 84 (2002) 69 74.
29) K. Tomishige, S. Kanazawa, S. Ito, K. Kunimori, Appl. Catal. A: Gen. 244 (2003) 71 82.
30) B.Li, S. Kado, Y. Mukainakano, M. Nurunnabi, T. Miyao, S. Naito, K. Kunimori, K.
Tomishige, Appl. Catal. A: Gen. 304 (2006) 62 71.
31) Y. Mukainakano, B. Li, S. Kado, T. Miyazawa, K. Okumura, T. Miyao, S. Naito, K.
Kunimori, K. Tomishige, Appl. Catal. A: Gen. 318 (2007) 252 264.
32) Y. Mukainakano, K. Yoshida, S. Kado, K. Okumura, K. Kunimori, K. Tomoshige, Chem. Eng. Sci. 63 (2008) 4891 4901.
33) Y. Mukainakano, K. Yoshida, K. Okumura, K. Kunimori, K. Tomoshige, Catal. Today 132 (2008) 101 108.
34) K. Yoshida, N. Begum, S. Ito, K. Tomishige, Appl. Catal. A: Gen. 358 (2009) 186 192.
35) K. Tomishige, J. Jpn. Petrol. Inst. 50 (2007) 287 298.
36) J. Nishikawa, T. Miyazawa, K. Nakamura, M. Asadullah, K. Kunimori, K. Tomishige, Catal. Commun. 9 (2008) 195 201.
37) D. Mukai, Y. Murai, T. Higo, S. Ogo, Y. Sugiura, Y. Sekine, Appl. Catal. A: Gen. 471 (2014) 157 164.
38) D. Mukai, S. Tochiya, Y. Murai, M. Imori, Y. Sugiura, Y. Sekine, Appl. Catal. A: Gen.
464 465 (2013) 78 86.
39) B. Li, S. Kado, Y. Mukainakano, T. Miyazawa, T. Miyao, S. Naito, K. Okumura, K.
Kunimori, K. Tomishige, J. Catal. 245 (2007) 144 155.
40) Y. Chen, O. Yamazaki, K. Tomishige, K. Kaoru, Catal. Lett. 39 (1996) 91 95.
41) M. Nurunnabi, K. Fujimoto, K. Suzuki, B. Li, S. Kado, K. Kunimori, K. Tomishige, Catal. Commun. 7 (2006) 73 78.
42) B. Pawalec, S. Damyanova, K. Arishtirova, J.L.G. Fierro, L. Petrov, Appl. Catal. A:
Gen. 323 (2007) 188 201.
117
0 10 20 30 40 50
0 50 100 150 200
Time on sream / min
with pre-reduction without pre-reduction
Fig. 1 H2 yield of time on stream on physically mixed catalyst (Pt/LSAO + Ni/LSAO) with and without pre-reduction42).
118
0 10 20 30 40 50 60
0 50 100 150 200
Time on stream / min
Pt/Ni/LSAO Ni/Pt/LSAO Pt-Ni/LSAO
Fig. 2 H2yield of time on stream on Pt/Ni/LSAO, Ni/Pt/LSAO and Pt-Ni/LSAO catalysts without pre-reduction42).
119
860 865
870 875
880 885
890 895
900
Binding energy / eV
Ni 2p
1/2Ni/LSAO as made Ni/LSAO after reduction
Ni/Pt/LSAO as made Pt-Ni/LSAO as made
Fig. 3 XPS spectra of Ni 2p1/2on Ni/Pt/LSAO (as made) and Pt-Ni/LSAO (as made)37).
120
11540 11560 11580 11600
PtO
2Pt foil Pt/LSAO as made Pt/Ni/LSAO as made
Fig. 4 XANES spectra of Pt L -edge on Pt/Ni/LSAO (as made) and Pt/LSAO (as made).
121
400 500 600 700 800 900 1000 1100
Temperature / K
Ni/LSAO
Pt/Ni/LSAO Ni/Pt/LSAO
Fig. 5 H2-TPR spectra of Ni/LSAO, Pt/Ni/LSAO, and Ni/Pt/LSAO.
122
0 5 10 15 20 25 30
1 3 5 7 9 11 13 15 17 19 21 23 25 Particle size / nm
Ni/LSAO
Total count: 125 Mean particle size:
12.8 nm
0 20 40 60 80 100
1 3 5 7 9 11 13 15 17 19 21 23 25 Particle size / nm
Total count: 140 Mean particle size:
3.2 nm
Pt/Ni/LSAO
0 10 20 30 40 50
1 3 5 7 9 11 13 15 17 19 21 23 25 Particle size / nm
Total count: 121 Mean particle size:
5.4 nm
Ni/Pt/LSAO
0 10 20 30 40 50 60
1 3 5 7 9 11 13 15 17 19 21 23 25 Particle size / nm
Total count: 146 Mean particle size:
5.6 nm
Pt-Ni/LSAO
Fig. 6 Metal particle size distribution over Ni/LSAO, Pt/Ni/LSAO, Ni/Pt/LSAO, and Pt-Ni/LSAO catalysts.
123
Table 1 Catalytic performance of Ni/LSAO and Pt/Ni/LSAO with or without pre-reduction: C1 yield, selectivity to each gas component, and H2 yield are values at 10 min of reaction42).
C1yield / %
Selectivity / %
H2yield / %
Coke formation /
mg g-cat-1
Ratio of coke formation to gas
formation / 10-4
CO CH4 CO2
Ni/LSAO (with
pre-reduction) 57.5 33.7 3.3 63.0 48.4 57 17.5
Pt/Ni/LSAO (with
pre-reduction) 57.4 27.6 4.4 68.0 49.4 10 3.0
Pt/Ni/LSAO (without
pre-reduction) 59.1 32.6 3.9 63.5 52.7 8 2.4
124
Table 2 Catalytic performance of bimetallic catalysts between Pt and Ni without pre-reduction: C1 yield, selectivity to each gas component, and H2 yield are values at 10 min of reaction42).
C1yield / %
Selectivity / %
H2yield / %
Coke formation /
mg g-cat-1
Ratio of coke formation to gas
formation / 10-4
CO CH4 CO2
Pt/Ni/LSAO 59.1 32.6 3.9 63.5 52.7 8 2.4
Ni/Pt/LSAO 51.2 30.3 1.5 68.2 48.1 69 22.2
Pt-Ni/LSAO 48.1 33.0 3.8 63.2 46.5 9 3.2
125
Table 3 Curve fitting parameters for EXAFS spectra on Pt/Ni/LSAO after each treatment42).
Catalyst Shell CN R/ Å dE/ eV DW / Å Rf/ %
Pt/Ni/LSAO as made Pt-O 6.95 2.07 -0.13 0.083 0.44
Pt/Ni/LSAO after reduction Pt-Pt 4.12 2.66 -10.00 0.071 0.005
Pt-Ni 7.88 2.56 7.57 0.11
Pt/Ni/LSAO after reaction Pt-Pt 8.08 2.66 -10.00 0.060 0.018
Pt-Ni 3.68 2.53 1.82 0.12
126
Table 4 Surface atomic concentrations on Pt/Ni/LSAO and Ni/Pt/LSAO catal ysts measured by XPS: pre-reduction was conducted by H2at 873 K for 0.5 h.
Surface concentration /
-Pt Ni La Sr Al O Pt/Ni /
-(Pt + Ni)/Al / -Pt/Ni/LSAO
(red) 0.005 0.064 0.049 0.098 0.134 0.650 0.078 0.515
Ni/Pt/LSAO
(red) 0.003 0.068 0.054 0.087 0.135 0.653 0.044 0.526
127
6
-2 Ni ( )
NiOx NiOx LaAlO3 -Al2O3
Ni/LaAlO3 Pd
673 K Ni Ni/ -Al2O3 Co
Ni/Co 723 K 648 K
3 Pt La1-xSrxAlO
3-( ) XPS EXAFS
Pt
Pt Sr
4 Ni La0.7Sr0.3AlO
3-XRD
XPS Sr
Ni- H2O
redox Ni/
5 Ni/La0.7Sr0.3AlO3- Pt
XPS
Pt Ni Pt Ni
Ni STEM EXAFS
XPS Pt Ni
(Pt Ni )
-128
2
1.
1.1
SiO2 JRC-SIO-7 SiO2 (
) ( ) (Wako Pure Chemical Industries Ltd.)
(Kanto Chemical Co. Inc.) (Soekawa
Chemical Co., Ltd.) (Kanto Chemical Co. Inc.)
1073 K 1 h Mo/SiO2 V/SiO2 Fe/SiO2 Ag/SiO2
MoO3 11.2 wt% V2O5 7.4 wt% Fe2O3 6.3 wt%
Ag2O 9.2 wt% BaO SrO La2O3
3 (Kanto
Chemical Co. Inc.) (Kanto
Chemical Co. Inc.) 353 K 16 h
1 h 673 K 2 h 1123 K 10 h
Nb2O5 WO3 Kanto Chemical Co. Inc.
Fe/Nb2O5 Fe/SiO2
Fe2O3 1.6 wt%
1.2
Fig. 1 CH4 :
O2: Ar = 12. 5 : 6.3 : 81.2 vol% ( 400 mL min-1) 80 mg
H2:Ar = 10 : 90 vol% ( 100 mL min-1) 1023
K 0.5 h GC-FID
CH4
Fe/SiO2 1023 K
CH4 : Ar = 12.5 : 87.5 vol% ( 400 mL min-1)
O2: Ar = 6.7 : 93.3 vol% ( 375 mL min-1) 15 min
129
Ar 0 10 120 sec