SupplementaryInformation
Low-temperaturesynthesis of Ruddlesden-Popper type layered perovskite LaxCa3-xMn2O7 for methane combustion
Xiaorui Du a,b, GuojunZoua,*, Xiaolai Wang a,*
a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PRChina
bUniversity of Chinese Academy of Sciences, Beijing 100049, PR China
*Corresponding authors. Tel.: +86 0931 4968308; fax: +86 931 8277088. E-mail addresses: (G. Zou); (X. Wang).
Table S1. The Miller indices corresponding to the X-ray diffraction peaks of LaxCa3-xMn2O7
a The experimental d values.
b The calculated Miller indices based on thedexp values and the lattice spacing formula. The space group was set to be I4/mmm, and the lattice spacing formula was.
cThe quasi d values calculated in turn based on the obtained lattice parameters and Miller indices.
The dcal values were consistent with the dexp values substantially, demonstrating that the space group and lattice parameters were set appropriately.
(a)x = 0.8, La0.8Ca2.2Mn2O7, a = b = 3.8398 Å, c = 19.2367 Å
2θ (degree) / dexpa(Å) / Miller Index (hkl)b / dcalc (Å)18.459 / 4.8024 / (0 0 4) / 4.8092
23.148 / 3.8391 / (1 0 0) / 3.8398
29.122 / 3.0637 / (1 0 4) / 3.0007
33.06 / 2.7072 / (1 1 0) / 2.7151
(1 0 5) / 2.7178
34.389 / 2.6056 / (1 1 2) / 2.6130
36.509 / 2.4590 / (1 0 6) / 2.4610
40.684 / 2.2158 / (1 0 7) / 2.2347
44.345 / 2.0410 / (116) / 2.0720
47.28 / 1.9209 / (00 10) / 1.9237
47.814 / 1.9007 / (200) / 1.9199
51.154 / 1.7841 / (2 04) / 1.7831
54.558 / 1.6806 / (1 1 9) / 1.6795
58.99 / 1.5644 / (1110) / 1.5696
59.568 / 1.5506 / (2 15) / 1.5681
64.707 / 1.4393 / (2 17) / 1.4563
69.075 / 1.3586 / (2010) / 1.3589
69.91 / 1.3444 / (220) / 1.3576
72.864 / 1.2970 / (3 0 0) / 1.2799
78.324 / 1.2197 / (3 0 5) / 1.2145
(3 1 0) / 1.2143
(b)x = 1.0, LaCa2Mn2O7, a = b = 3.8411 Å, c = 19.5217 Å
2θ (degree) / dexpa(Å) / Miller Index (hkl)b / dcalc (Å)18.099 / 4.8971 / (0 0 4) / 4.8804
23.11 / 3.8453 / (1 0 0) / 3.8411
29.043 / 3.0719 / (1 04) / 3.0184
32.871 / 2.7223 / (110) / 2.7161
(1 0 5) / 2.7382
34.286 / 2.6132 / (1 1 2) / 2.6167
36.244 / 2.4764 / (1 0 6) / 2.4827
37.635 / 2.3880 / (1 1 4) / 2.3733
40.307 / 2.2356 / (1 0 7) / 2.2567
47.056 / 1.9295 / (2 0 0) / 1.9206
50.916 / 1.7919 / (2 0 4) / 1.7872
53.071 / 1.7241 / (2 0 5) / 1.7233
54.133 / 1.6928 / (1 1 9) / 1.6949
58.486 / 1.5767 / (2 1 5) / 1.5723
60.114 / 1.5379 / (2 1 6) / 1.5191
62.756 / 1.4793 / (2 1 7) / 1.4626
68.481 / 1.3689 / (2 0 10) / 1.3691
68.71 / 1.3649 / (2 2 0) / 1.3580
74.201 / 1.2769 / (2 2 5) / 1.2827
77.801 / 1.2266 / (3 0 5) / 1.2166
78.219 / 1.2211 / (3 1 0) / 1.2147
82.776 / 1.1650 / (3 1 5) / 1.1598
86.834 / 1.1207 / (2 2 10) / 1.1148
(c)x = 1.2, LaCa2Mn2O7, a = b = 3.8421 Å, c = 19.3216 Å
2θ (degree) / dexpa(Å) / Miller Index (hkl)b / dcalc (Å)23.099 / 3.8471 / (1 0 0) / 3.8421
26.901 / 3.3114 / (1 0 3) / 3.2996
32.997 / 2.7122 / (1 1 0) / 2.7168
(1 0 5) / 2.7246
37.511 / 2.3956 / (1 1 4) / 2.3679
40.782 / 2.2107 / (1 0 7) / 2.2417
47.203 / 1.9238 / (2 0 0) / 1.9211
(0010) / 1.9322
53.137 / 1.7221 / (205) / 1.7202
53.963 / 1.6977 / (1 1 9) / 1.6844
58.97 / 1.5649 / (2 1 5) / 1.5700
64.454 / 1.4444 / (2 17) / 1.4587
67.557 / 1.3854 / (2 18) / 1.4001
68.866 / 1.3622 / (2 010) / 1.3623
(22 0) / 1.3584
73.603 / 1.2858 / (3 0 0) / 1.2807
78.631 / 1.2157 / (3 0 5) / 1.2157
78.995 / 1.2110 / (3 1 0) / 1.2150
82.694 / 1.1660 / (3 1 5) / 1.1590
88.5 / 1.1038 / (2 2 10) / 1.1112
(d)x = 1.5, La1.5Ca1.5Mn2O7, a = b = 3.8742 Å, c = 19.3421 Å
2θ (degree) / dexpa(Å) / Miller Index (hkl)b / dcalc (Å)22.954 / 3.8711 / (1 0 0) / 3.8742
29.806 / La2O3
32.76 / 2.7313 / (1 05) / 2.7374
(1 1 0) / 2.7395
37.258 / 2.4113 / (0 0 8) / 2.4178
40.401 / 2.2306 / (1 0 7) / 2.2496
47.028 / 1.9306 / (0 0 10) / 1.9342
47.138 / 1.9263 / (2 0 0) / 1.9371
48.184 / 1.8869 / (1 0 9) / 1.8793
52.873 / 1.7301 / (2 1 1) / 1.7257
53.815 / 1.7020 / (1 2 2) / 1.7054
58.333 / 1.5805 / (2 1 5) / 1.5812
58.639 / 1.5730 / (1 1 10) / 1.5801
64.114 / 1.4512 / (2 1 7) / 1.4679
68.699 / 1.3651 / (2 2 0) / 1.3697
69.016 / 1.3596 / (2 0 10) / 1.3687
73.364 / 1.2894 / (0 3 1) / 1.2885
78.046 / 1.2233 / (3 1 0) / 1.2251
82.742 / 1.1654 / (3 1 5) / 1.1680
(e)x = 2.0, La2CaMn2O7, a = b = 3.8768 Å, c = 21.0472 Å
2θ (degree) / dexpa(Å) / Miller Index (hkl)b / dcalc (Å)17.017 / 5.2059 / (0 0 4) / 5.2618
22.992 / 3.8648 / (1 0 0) / 3.8768
26.012 / 3.4225 / (1 0 3) / 3.3932
27.975 / 3.1867 / (1 0 4) / 3.1211
29.024 / La2O3
29.882 / La2O3
32.728 / 2.7339 / (1 1 0) / 2.7413
37.219 / 2.4137 / (1 1 4) / 2.4312
39.404 / La2O3
40.383 / 2.2316 / (1 0 8) / 2.1770
45.973 / La2O3
47.035 / 1.9303 / (2 0 0) / 1.9384
48.635 / 1.8705 / (2 0 3) / 1.8684
52.088 / La2O3
52.965 / 1.7273 / (2 1 0) / 1.7338
55.695 / 1.6489 / (2 1 4) / 1.6467
58.5 / 1.5764 / (2 1 5) / 1.6031
68.731 / 1.3646 / (2 2 0) / 1.3707
78.321 / 1.2197 / (3 1 0) / 1.2260
82.829 / 1.1644 / (2 2 10) / 1.1486
(3 1 5) / 1.1770
87.423 / 1.1146 / (2 2 11) / 1.1143
(f)x = 2.5, La2.5Ca0.5Mn2O7, a = b = 3.8861 Å, c = 21.9563 Å
2θ (degree) / dexpa(Å) / Miller Index (hkl)b / dcalc (Å)22.864 / 3.8861 / (1 0 0) / 3.8861
26.062 / 3.4161 / (1 0 3) / 3.4323
29.098 / La2O3
29.911 / La2O3
32.683 / 2.7376 / (1 1 0) / 2.7479
39.491 / La2O3
40.275 / 2.2373 / (1 0 8) / 2.2418
46.084 / La2O3
46.893 / 1.9358 / (2 0 0) / 1.9431
52.199 / La2O3
52.898 / 1.7293 / (2 1 0) / 1.7379
55.475 / 1.6550 / (2 1 4) / 1.6569
58.391 / 1.5791 / (2 1 5) / 1.6160
62.205 / La2O3
68.585 / 1.3671 / (2 2 0) / 1.3739
72.058 / 1.3095 / (3 0 0) / 1.2954
73.207 / 1.2918 / (3 0 1) / 1.2931
75.209 / 1.2623 / (3 0 4) / 1.2607
78.08 / 1.2229 / (3 1 0) / 1.2289
82.515 / 1.1680 / (3 1 5) / 1.1647
87.011 / 1.1189 / (2 2 11) / 1.1317
(g)x = 3.0, La3Mn2O7+δ, a = b = 3.8870 Å, c = 22.4135 Å
2θ (degree) / dexpa(Å) / Miller Index (hkl)b / dcalc (Å)22.859 / 3.8870 / (1 0 0) / 3.8870
25.994 / 3.4249 / (1 0 3) / 3.4482
30.109 / 2.9655 / (1 0 5) / 2.9367
32.683 / 2.7376 / (1 1 0) / 2.7485
40.106 / 2.2464 / (1 0 8) / 2.2728
40.514 / 2.2247 / (1 1 6) / 2.2139
42.815 / 2.1103 / (1 0 9) / 2.0969
46.793 / 1.9397 / (2 0 0) / 1.9435
52.743 / 1.7341 / (2 1 0) / 1.7383
55.39 / 1.6573 / (2 1 4) / 1.6603
58.123 / 1.5857 / (2 1 5) / 1.6207
58.648 / 1.5727 / (2 1 6) / 1.5760
68.025 / 1.3770 / (2 2 0) / 1.3743
68.689 / 1.3653 / (2 2 1) / 1.3717
73.001 / 1.2949 / (3 0 0) / 1.2957
77.609 / 1.2291 / (3 1 0) / 1.2292
78.023 / 1.2236 / (3 1 1) / 1.2273
82.297 / 1.1706 / (2 2 10) / 1.1716
86.608 / 1.1230 / (2 2 11) / 1.1393
Fig. S1. XPS spectra of La3d, Mn2p, and Ca2p for the LaxCa3-xMn2O7samples.