Calculation of the Chemical Compositions of Movfeo-EA and Movwo-EA Was Conducted in This Paper

Supplementary

Calculation of the chemical compositions of MoVFeO-EA and MoVWO-EA was conducted in this paper.

(i) Composition of metals of MoVFeO-EA and MoVWO-EA.

Prior to the calculation, Fe is assumed to be placed at the heptagonal channel and W is assumed to be placed at the {Mo6O21}6- pentagonal unit. Since the structural network (comprised of Mo and V) per unit cell of Mo3VOx is comprised of 27 metals and 75 oxygens (reference 8), the allocation of Mo, V, M3rd can be performed with the result of ICP.

MoVFeO-EA

The ratio of elements based on Mo was Mo/V/Fe = 1/0.30/0.06. In this case, structural network is comprised of Mo and V. Fe is placed in the channel. Thus, the number of Mo, V, and Fe in the structural unit cell is calculated as 20.8, 6.2, and 1.2, respectively.

MoVWO-EA

The ratio of elements based on Mo was Mo/V/W = 1/0.29/0.06. In this case, structural network is comprised of Mo, V, and W. Thus, the number of Mo, V, and W is calculated as 20, 5.8, and 1.2, respectively.

(ii) The number of counter cations

The C/H/N ratios obtained by CHN elemental analysis were 1.28/1.10/1.01 and 1.29/0.97/1.01 for MoVFeO-EA and MoVWO-EA, respectively. If it is assumed that C is all derived from EtNH3+, that N is derived from EtNH3+ and NH4+, and that H is derived from EtNH3+, NH4+, and H2O, the chemical composition of MoVFeO-EA and MoVWO-EA can be calculated as Mo20.8V6.2Fe1.2O75(EtNH3)x(NH4)y・zH2O and Mo20.0V5.8W1.2O75(EtNH3)x(NH4)y・zH2O, respectively, where x, y, and z correspond to the number of EtNH3+, NH4+, and H2O per structural unit cell. Therefore, the molecular weight of the structural unit cell of MoVFeO-EA (MMoVFeO-EA) and MoVWO-EA (MMoVWO-EA) can be calculated as (MMo×20.8+MV×6.2+MFe×1.2+Mox×75+MEtNH3×x+MNH4×y+MH2O×z) and (MMo×20.8+MV×5.8+MFe×1.2+Mox×75+MEtNH3×x+MNH4×y+MH2O×z)}, respectively, where MMo, MV, MFe, MW, Mox,MEtNH3, MNH4, and MH2O represent the molecular weight of Mo, V, Fe, W, O, EtNH3+, NH4+, and H2O, respectively.

Since the weight percentages of C, H, N were determined by CHN elemental analysis for MoVFeO-EA and MoVWO-EA, we can make the following equations.

MoVFeO-EA

100×24x / MMoVFeO-EA = 1.28(1)

100×(14x+14y) / MMoVFeO-EA = 1.01(2)

100×(8x+4y+2z) / MMoVFeO-EA = 1.10(3)

MoVWO-EA

100×24x / MMoVWO-EA = 1.29(4)

100×(14x+14y) / MMoVWO-EA = 0.97(5)

100×(8x+4y+2z) / MMoVWO-EA = 1.10(6)

From the (1), (2), and (3), the number of counter cations and water per structural unit cell can be determined for MoVFeO-EA. From the (4), (5), and (6), the number of counter cations and water per structural unit cell can be determined for MoVWO-EA.

Fig. S1 XRD patterns of MoVWO-EA-fresh synthesized by using H2WO4 (a) or (NH4)6[H2W12O]・nH2O(b) as a W source.

Fig. S2 XPS spectra of MoVO-A ((a) Mo, (b) V), MoVFeO-EA ((c) Mo, (d) V, (e) Fe) and MoVWO-EA ((f) Mo, (g) V, (h) W).

Fig. S3 (A) IR spectra of MoVO-A (a), MoVFeO-EA (b), and MoVWO-EA (c). (B) Enlarged IR spectra from 1000 cm-1 to 1550 cm-1. Black dot line represents the absorption derived from NH4+ and red dot line represents the absorption derived from alkylammonium cation.

Fig. S4 TPD (A) and TPO (B) spectra of MoVFeO-EA and TPD (C) and TPO (D) spectra of MoVWO-EA. Mass fragment: m/z = 16, NH3; m/z = 44, CO2; m/z = 45, C2H5NH2.

Fig. S5 (A) Structural model obtained by Rietveld refinement. Mo, light green; V, gray; O, red. (B) Difference (black), calculated (blue line), and observed (red circle) patterns obtained by Rietveld refinement for MoVO-A-AC. XRD peaks of 27.8~28.8°, 47~48°, 56~56.5°, 69~69.5°, and 76~77° were attributed to Si added in order to remove orientation effects and were excluded from Rietveld refinement. Rwp value of the refinement was 11.6%.

Fig. S6 (A) N2 adsorption isotherm of MoVO-A-AC (circle), MoVFeO-EA-AC (triangle), and MoVWO-EA-AC (square). (B) Representation of microporosity of MoVO-A-AC (circle), MoVFeO-EA-AC (triangle), and MoVWO-EA-AC (square).

Table S1. Refined parameters and agreement factors of Rietveld refinement for MoVO-A-AC

MoVO-A-AC
Crystal system / Trigonal
Space group / P3
a /Å / 21.25
c /Å / 4.007
 =  /deg / 90
 /deg / 120
V /Å3 / 1570.0
Agreement factors
Rwp /% / 11.6
Rwp (without background) /% / 25.9
Rp /% / 8.8
Pattern parameter / Pseudo Voigt
Peak shape function
FWHM / U = 3.54043, V = -1.35744, W = 0.14073
Profile parameter / NA = 0.99988, NB = -0.00000
Line shift
Instrument geometry / Bragg-Brentano
Zero point / -1.87269
Shift #1 / 1.77178
Shift#2 / 0.35010
Asymmetry
Correction method / Berar-Baldinozzi
Parameter / P1 = -0.58081, P2 = -0.16245, P3 = 1.05502, P4 = 0.30114

Table S2. Atomic coordinates and occupancy of the framework of MoVO-A-AC

Site / x / y / z / Occupancy / Mo/(Mo+V)
Mo1 / 0.17054 / 0.13503 / 0.00192 / 1.0 / 1
Mo2 / 0.22003 / 0.33221 / -0.01728 / 1.0 / 1
Mo3 / 0.33284 / 0.55877 / 0.02391 / 0.66 / 0.85
Mo4 / 0.42466 / 0.46077 / -0.02123 / 1.0 / 1
Mo5 / 0.50875 / 0.29551 / 0.00970 / 1.0 / 1
V6 / 0.61763 / 0.49039 / 0.24262 / 1.0
Mo7 / 0.77663 / 0.66947 / -0.06344 / 1.0 / 1
V8 / 0.81441 / 0.85113 / 0.13195 / 1.0
Mo9 / 0.34840 / 0.27271 / 0.20016 / 1.0 / 1
O1 / 0.16698 / 0.13460 / 0.54886 / 1.0
O2 / 0.21927 / 0.33366 / 0.55303 / 1.0
O3 / 0.33276 / 0.56400 / 0.47902 / 1.0
O4 / 0.42694 / 0.45855 / 0.52576 / 1.0
O5 / 0.50548 / 0.29592 / 0.53953 / 1.0
O6 / 0.62029 / 0.49142 / 0.53000 / 1.0
O7 / 0.78171 / 0.67358 / 0.53200 / 1.0
O8 / 0.80496 / 0.84975 / 0.54093 / 1.0
O9 / 0.34598 / 0.27073 / 0.55023 / 1.0
O10 / 0.09564 / 0.13847 / 0.06470 / 1.0
O11 / 0.13753 / 0.03984 / 0.05470 / 1.0
O12 / 0.12281 / 0.28452 / 0.06470 / 1.0
O13 / 0.23522 / 0.24766 / 0.04314 / 1.0
O14 / 0.25540 / 0.44263 / 0.01855 / 1.0
O15 / 0.27310 / 0.16116 / 0.04639 / 1.0
O16 / 0.24930 / 0.58850 / -0.01838 / 1.0
O17 / 0.33014 / 0.36273 / 0.04599 / 1.0
O18 / 0.39554 / 0.21351 / 0.03512 / 1.0
O19 / 0.41103 / 0.53604 / 0.00855 / 1.0
O20 / 0.45067 / 0.36612 / 0.04083 / 1.0
O21 / 0.53011 / 0.21932 / 0.05470 / 1.0
O22 / 0.53473 / 0.49897 / 0.04470 / 1.0
O23 / 0.58326 / 0.39458 / 0.04470 / 1.0
O24 / 0.68355 / 0.59017 / 0.05470 / 1.0
O25 / 0.76241 / 0.74287 / 0.04470 / 1.0

Table S3. Refined parameters and agreement factors of Rietveld refinement for MoVFeO-EA-AC

MoVFeO-EA-AC
Crystal system / Trigonal
Space group / P3
a /Å / 21.31
c /Å / 4.009
 =  /deg / 90
 /deg / 120
V /Å3 / 1576.6
Agreement factors
Rwp /% / 10.5
Rwp (without background) /% / 26.5
Rp /% / 7.5
Pattern parameter / Pseudo Voigt
Peak shape function
FWHM / U = 2.18453, V = -0.92378, W = 0.10623
Profile parameter / NA = 1.00318, NB = -0.00079
Line shift
Instrument geometry / Bragg-Brentano
Zero point / -1.83170
Shift #1 / 1.75184
Shift#2 / 0.29661
Asymmetry
Correction method / Berar-Baldinozzi
Parameter / P1 = -1.19653, P2 = -0.36870, P3 = 2.28643, P4 = 0.71582

Table S4. Atomic coordinates and occupancy of the framework of MoVFeO-EA-AC

Site / x / y / z / Occupancy / Mo/(Mo+V)
Mo1 / 0.17275 / 0.13801 / 0.03295 / 1.0 / 1
Mo2 / 0.22276 / 0.33446 / -0.07135 / 1.0 / 1
Mo3 / 0.29728 / 0.55347 / 0.00938 / 0.66 / 0.85
Mo4 / 0.42156 / 0.45249 / -0.01848 / 1.0 / 1
Mo5 / 0.51127 / 0.29715 / -0.05053 / 1.0 / 1
V6 / 0.61148 / 0.49720 / 0.35276 / 1.0
Mo7 / 0.77727 / 0.66930 / -0.07873 / 1.0 / 1
V8 / 0.81108 / 0.84641 / 0.10165 / 1.0
Mo9 / 0.34426 / 0.26397 / 0.17182 / 1.0 / 1
Fe / 0.11406 / 0.49858 / 0.96269 / 0.4
O1 / 0.16652 / 0.13245 / 0.52301 / 1.0
O2 / 0.21879 / 0.33150 / 0.52718 / 1.0
O3 / 0.30025 / 0.54775 / 0.47902 / 1.0
O4 / 0.42636 / 0.45624 / 0.50033 / 1.0
O5 / 0.50502 / 0.29380 / 0.51369 / 1.0
O6 / 0.61090 / 0.49142 / 0.53000 / 1.0
O7 / 0.78002 / 0.67402 / 0.50615 / 1.0
O8 / 0.81038 / 0.84776 / 0.54093 / 1.0
O9 / 0.34552 / 0.26859 / 0.52438 / 1.0
O10 / 0.09564 / 0.13847 / 0.06470 / 1.0
O11 / 0.13753 / 0.03984 / 0.05470 / 1.0
O12 / 0.12281 / 0.28452 / 0.06470 / 1.0
O13 / 0.23475 / 0.24550 / 0.01729 / 1.0
O14 / 0.22830 / 0.43378 / 0.01855 / 1.0
O15 / 0.27265 / 0.15901 / 0.02054 / 1.0
O16 / 0.24243 / 0.59445 / -0.01838 / 1.0
O17 / 0.32967 / 0.36059 / 0.02014 / 1.0
O18 / 0.39508 / 0.21138 / 0.00927 / 1.0
O19 / 0.39477 / 0.52791 / 0.00855 / 1.0
O20 / 0.45020 / 0.36398 / 0.01498 / 1.0
O21 / 0.53011 / 0.21932 / 0.05470 / 1.0
O22 / 0.53473 / 0.49897 / 0.04470 / 1.0
O23 / 0.58326 / 0.39458 / 0.04470 / 1.0
O24 / 0.68355 / 0.59017 / 0.05470 / 1.0
O25 / 0.76241 / 0.74287 / 0.04470 / 1.0

Table S5. Refined parameters and agreement factors of Rietveld refinement for MoVWO-EA-AC

MoVWO-EA-AC
Crystal system / Trigonal
Space group / P3
a /Å / 21.29
c /Å / 3.997
 =  /deg / 90
 /deg / 120
V /Å3 / 1569.4
Agreement factors
Rwp /% / 10.4
Rwp (without background) /% / 23.6
Rp /% / 7.6
Pattern parameter / Pseudo Voigt
Peak shape function
FWHM / U = 1.78838, V = -0.65621, W = 0.06911
Profile parameter / NA = 1.00114, NB = -0.00029
Line shift
Instrument geometry / Bragg-Brentano
Zero point / -0.99170
Shift #1 / 0.93455
Shift#2 / 0.20305
Asymmetry
Correction method / Berar-Baldinozzi
Parameter / P1 = 0.20652, P2 = -0.01047, P3 = -0.56056, P4 = -0.00982

Table S6. Atomic coordinates and occupancy of the framework of MoVWO-EA-AC

Site / x / y / z / Occupancy / Mo/(Mo+V) / Mo/(Mo+W)
Mo1 / 0.16477 / 0.13216 / 1.94443 / 1.0 / 1 / 0.93
Mo2 / 0.23404 / 0.33692 / 1.97991 / 1.0 / 1 / 0.93
Mo3 / 0.36344 / 0.57758 / -0.00639 / 0.70 / 0.85 / 1
Mo4 / 0.43089 / 0.45727 / 0.96359 / 1.0 / 1 / 0.93
Mo5 / 0.50283 / 0.29880 / 2.00737 / 1.0 / 1 / 0.93
V6 / 0.62630 / 0.48831 / 1.14468 / 1.0
Mo7 / 0.33516 / 0.11319 / 1.98873 / 1.0 / 1 / 1
V8 / 0.80099 / 0.84641 / 1.21936 / 1.0
Mo9 / 0.33674 / 0.26486 / 1.19132 / 1.0 / 1 / 0.93
O1 / 0.16617 / 0.13291 / 0.53797 / 1.0
O2 / 0.23116 / 0.33857 / 0.54215 / 1.0
O3 / 0.35988 / 0.57213 / 0.44872 / 1.0
O4 / 0.43330 / 0.46146 / 0.51487 / 1.0
O5 / 0.49653 / 0.29613 / 0.52865 / 1.0
O6 / 0.62844 / 0.48844 / 0.53000 / 1.0
O7 / 0.78083 / 0.66843 / 0.52111 / 1.0
O8 / 0.80496 / 0.85445 / 0.54093 / 1.0
O9 / 0.33678 / 0.26550 / 0.53934 / 1.0
O10 / 0.09564 / 0.13847 / 0.06470 / 1.0
O11 / 0.13753 / 0.03984 / 0.05470 / 1.0
O12 / 0.13911 / 0.29267 / 0.06470 / 1.0
O13 / 0.23125 / 0.25169 / 0.03225 / 1.0
O14 / 0.27985 / 0.46427 / 0.01855 / 1.0
O15 / 0.26702 / 0.15250 / 0.03550 / 1.0
O16 / 0.26452 / 0.58193 / -0.04869 / 1.0
O17 / 0.33943 / 0.37145 / 0.03510 / 1.0
O18 / 0.39487 / 0.21982 / 0.02423 / 1.0
O19 / 0.43276 / 0.53279 / 0.00855 / 1.0
O20 / 0.43587 / 0.34905 / 0.02994 / 1.0
O21 / 0.53571 / 0.24665 / 0.05470 / 1.0
O22 / 0.55102 / 0.50712 / 0.04470 / 1.0
O23 / 0.57783 / 0.38716 / 0.04470 / 1.0
O24 / 0.69025 / 0.58473 / 0.05470 / 1.0
O25 / 0.76241 / 0.74287 / 0.04470 / 1.0

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