Supporting Information
Reactivity of the Fe2O3(0001) Surface for Methane Oxidation: A
GGA+U Study
Jia-Jun Tang and Bin Liu*
Department of Chemical Engineering, Kansas State University, Manhattan, Kansas, 66506
S1
Table of Contents
1. Surface Energy Calculations (page S3)
2. Surface Relaxation (page S6)
3. Electronic Structures of CH4 C–H Bond Activation (page S7)
4. Determination of the Energy Barriers of C–O Bond Formations, forming CH2O*
and CHO*, using the BEP Relationship (page S9)
5. Calculated Vibrational Frequencies (page S10)
6. References (page S19)
S2
1. Surface Energy Calculations
In order to determine surface termination relative stabilities, we considered up to
six possible surface terminations: Fe-Fe-O3, O1-Fe-Fe, O2-Fe-Fe, O3-Fe-Fe, Fe-O3-Fe,
and O-Fe-O3. Configurations are illustrated in Figure S1. In these models, p(1 × 1)
surface was adopted with at least six stoichiometric Fe2O3 layers. Atoms in the middle
Fe2O3 layer were fixed, while the other atoms were allowed to relax, thereby creating
two surfaces in each model. The number of layers was thick enough for surface
energy calculations.
Figure S1. Side and top views of relaxed structures of Fe2O3(0001) surfaces with
different terminations, including (a) Fe-Fe-O3-, (b) O1-Fe-Fe-, (c) O2-Fe-Fe-, (d)
O3-Fe-Fe-, (e) Fe-O3-Fe-, and (f) O-Fe-O3-. Fe and O atoms are denoted by purple
and red balls. Top views are shown with depth cue. The numbers of Fe and O atoms in
six terminations are (16, 21), (12, 17), (12, 19), (12, 21), (14, 21), and (14, 23),
respectively.
Surface free energy can be described as,
Gsurf =
1
(Gslab − m ⋅ µ Fe − n ⋅ µ O ) ,
2A
(1)
S3
where Gslab is the Gibbs free energy of the slab model used in our calculations, A is
the in-plane surface area, and m and n are the numbers of Fe and O atoms in the unit
cell, respectively.
Based on the thermodynamic approach,1 sufficient bulk material is available to act
as a thermodynamic reservoir, relations between Fe, O, and Fe2O3 bulk chemical
potentials can be written as
Fe 2 O3
2 µFe + 3µO = µbulk
.
(2)
According to previous literature,1-5 Gibbs free energies in Eqn. (1) can be
approximated as first-principle total energies, Etot, since contributions from the
entropy and work done by pressure are trivial for solid systems. In thermal
equilibrium, α-Fe2O3(0001) surface energy as function of oxygen chemical potential
(µO) can be expressed by Eqn. (3),6-8
Esurf =
1  tot 1
3

Fe2O3
 E − mµ bulk − (n − m) µO  ,
2A 
2
2

(3)
where Etot and µ Fe O are first-principles total energies of the slab model and the bulk
2
bulk
3
Fe2O3 formula unit, A is the surface area, and m and n are the numbers of Fe and O
atoms in the unit cell (see Figure S1). Oxygen chemical potential was treated as a
tunable parameter to account for the ambient environment to which the surface was
exposed.
For the surface energy calculation of Fe-Fe-O3- termination with GGA method, the
S4
slab total energy, Etot, and the bulk Fe2O3, µ Fe O , were -249.54 and -34.52 eV,
2
bulk
3
respectively. The unit cell area was 21.89 Å2, and the numbers of Fe and O atoms
were 16 and 21, respectively. Lower and upper limits of range of allowed O chemical
potentials were -7.96 and -4.93 eV, and the respective surface energies were 63.35 and
271.09 meV Å-2, as plotted in the black line in
Figure S2 (a). The upper limit was determined by the value of 1/2 EOtot2 , shown as 0
for the O relative chemical potential in
Figure S2.
Figure S2 shows results of hematite (α-Fe2O3) (0001) surface energies; all six
terminations were calculated with GGA + U and GGA. For GGA + U results, in a
very wide range of oxygen relative chemical potential, the Fe-O3-Fe- terminated
surface was the most stable with a surface energy of 78.88 meV Å-2 (1.26 J m-2).
When −1.5 ≤ ∆µO ≤ 0 , the surface energy advantage of Fe-O3-Fe- terminated surface
was more than 20 meV Å-2. In a very low range of oxygen relative chemical potential,
the Fe-Fe-O3- and O1-Fe-Fe- terminated surfaces showed stableness. When ∆µO
approached 0, the O-Fe-O3- and O2-Fe-Fe- terminated surfaces became competitively
stable. However, the Fe-O3-Fe- terminated surface continued to dominate with an
obvious energetic advantage. For GGA results, Fe-O3-Fe- termination was the most
stable in the ∆µO relative chemical potential range from O-poor endpoint to -0.78 eV.
In ranges from -0.78 eV to -0.43 eV and from -0.43 to 0 eV, the O-Fe-O3- (ferryl)
S5
termination and O3-Fe-Fe- showed highest stability, respectively.
Figure S2. Surface energy of six terminations as a function of O chemical potential
calculated with GGA + U or GGA.
2. Surface Relaxation
Figure S3 shows interlayer relaxations of three uniquely terminated surfaces as
compared to available experimental and theoretical studies to prove the legitimacy of
our models. Surface relaxations shown in these Fe atomic surface layers are in
qualitative agreement with these literatures, which confirms that our models are
sufficiently accurate for further calculations. The structurally optimized O-Fe-O3(ferryl)-terminated surface not shown in Figure S1 contained a surface O-Fe bond
length of 1.606 Å, which is in good agreement with previous theoretical6 and
experimental9 results.
S6
Figure S3. Interlayer relaxations of uniquely terminated hematite (0001) surfaces.
Experimental results of O3-Fe-Fe- and Fe-O3-Fe- terminations are from Ref. [10] and
Ref. [11]. First and second theoretical results are from Ref. [6] and Ref. [12],
respectively.
3. Electronic Structures of Methane C–H Bond Activation
Charge difference analyses were performed to further elucidate the catalytic role
of surface ferryl O in methane C–H bond activation. In the transition state of CH4 C–
H bond activation on the ferryl-group, O–H1 bond length was 1.26 Å. The electron
transfer between the surface and the methane is shown in
Figure S4 (a), where charge accumulations for H1, C, and CH4 are of 0.0889 e,
0.0102 e, and 0.0961 e, respectively, indicating charge transfer from ferryl-terminated
surface to CH4 molecule. Electrons were transferred into the methane antibonding
states and significantly weakened molecule stability and lowered the energy barrier
S7
for C–H bond cleavage. Therefore, the presence of a ferryl group facilitates charge
transfer between the surface and the methane.
The transition state of C–H bond activation of methane on clean α-Fe2O3(0001)
surface is illustrated in
Figure S4 (b). C–H1 bond length was 1.48 Å, indicating that the C–H1 bond was
broken though the charge accumulation of +0.1149 e on H1. However, this charge was
not transferred to the methane antibonding states; therefore, the working mechanism
differed from the C–H bond activation mechanism on the ferryl O.
Figure S4. Charge difference plot of transition states of CH4 C–H bond activation on
(a) O pre-adsorbed and (b) clean α-Fe2O3(0001) surfaces. Charge accumulation and
depletion are yellow and blue, respectively, with an isosurface of 0.008 e.
S8
4. Determination of the Energy Barriers of C–O Bond Formations, forming CH2O*
and CHO*, using BEP Relationship
We used the Brønsted-Evans-Polanyi (BEP) relationship13-15 to determine the C–O bond
formation (forming CH2O* and CHO*) transition state energies. In this approach, the
elementary steps are written in the exothermic direction. The transition state and final state
energies are referenced to the gas-phase reactants of the elementary step. Figure S5 shows
that the linear BEP relationship between the final state (EFS) and transition state (ETS)
energies based on the DFT calculations of the indicated elementary steps. The slope and
intercept of the C–O bond formation reactions are 0.97 eV and 1.05 eV with the standard
error of ~0.18 eV. Based on this relationship, the energy barriers of CH2* + O* (lattice) CH2O* + VO and CH* + O* (lattice) CHO* + VO are estimated to be 1.09 eV and 1.18 eV,
respectively.
Figure S5. Brønsted-Evans-Polanyi (BEP) relationships for C–O bond formation reactions.
Final state (EFS) and transition state (ETS) energies are relative to initial state gas phase
energies, where each corresponding surface reaction is represented in the exothermic
direction.
S9
5. Calculated Vibrational Frequencies
Vibrational frequency calculations have been adopted for the evaluation of the free
energies of various intermediates and transition states, as well as the confirmation of the
imaginary frequencies of the transition states. Table S1 lists the vibrational frequencies of the
main intermediates and transition states.
Table S1. Vibrational Frequencies of Reaction Intermediates and Transition States of
Elementary Reactions of Methane Oxidation on Fe2O3 (0001)
Intermediates or
Vibrational Frequencies (cm-1)
Transition States
CH4*
CH4* adsorbed on Ferryl O
3108.14, 3063.37, 3023.13, 2918.68, 1523.98 1510.71, 1313.77, 1297.47,
1249.75, 711.08, 705.25, 705.03, 704.14, 698.56, 697.60, 688.49, 680.98,
679.77, 678.72, 668.85, 667.64, 581.11, 562.53, 561.92, 560.98, 538.97,
538.27, 537.74, 527.53, 517.18, 515.64, 514.61, 513.50, 512.21, 496.37,
495.12, 494.16, 475.56, 469.82, 468.12, 463.05, 457.24, 456.01, 454.91,
444.18, 443.72, 432.36, 430.70, 430.43, 406.56, 396.88, 395.68, 394.64,
385.24, 377.90, 376.28, 375.72, 374.23, 373.29, 363.96, 362.71, 361.42,
346.79, 346.10, 344.03, 331.99, 331.49, 329.44, 316.18, 314.82, 314.09,
312.80, 309.90, 305.65, 303.84, 302.53, 299.47, 298.10, 295.37, 276.69,
275.99, 263.28, 251.52, 251.19, 250.38, 248.28, 247.96, 241.33, 239.34,
238.64, 202.61, 201.90, 201.24, 195.63, 195.10, 173.17, 165.98, 165.59,
164.26, 155.06, 153.48, 152.73, 151.07, 149.64, 149.51, 147.90, 142.87,
132.84, 131.89, 130.33, 123.96, 122.78, 118.11, 106.27, 72.65, 72.14, 66.18,
54.28, 41.44, 39.95, 21.97, 15.86
3096.10, 3094.67, 3092.76, 2986.35, 1506.73, 1505.56, 1286.21, 1282.65,
1278.58, 860.11, 703.41, 702.21, 696.96, 693.54, 691.42, 687.58, 673.78,
667.71, 665.54, 630.05, 609.57, 589.29, 555.40, 552.17, 551.49, 545.68,
528.10, 524.98, 519.56, 511.27, 510.82, 508.66, 497.91, 493.36, 489.57,
484.58, 481.83, 477.32, 470.51, 468.02, 467.23, 462.84, 448.56, 442.38,
436.11, 433.86, 429.33, 419.44, 417.63, 407.88, 390.63, 390.12, 388.87,
386.89, 380.59, 379.14, 378.21, 373.80, 371.65, 367.09, 356.83, 350.69,
350.27, 346.30, 344.58, 343.14, 329.38, 325.71, 323.09, 314.28, 312.18,
310.73, 308.47, 304.92, 303.72, 298.08, 296.37, 294.40, 288.80, 280.38,
278.79, 272.32, 260.46, 253.13, 248.63, 247.05, 245.34, 243.81, 239.21,
233.41, 207.31, 202.89, 201.60, 199.61, 197.94, 189.76, 174.75, 174.03,
171.19, 163.95, 158.79, 156.53, 155.40, 153.98, 151.16, 150.21, 141.59,
134.65, 133.97, 130.37, 129.23, 126.19, 124.49, 99.69, 92.94, 81.16, 78.27,
S10
77.93, 74.84, 71.85, 41.08
CH3*
CH2*
CH*
C*
3148.74, 3145.61, 2999.37, 1368.80, 1365.18, 984.71, 700.87, 699.80,
699.24, 695.92, 693.97, 690.34, 677.36, 676.44, 675.50, 667.42, 665.67,
648.59, 596.14, 595.04, 565.68, 559.27, 558.17, 557.15, 532.76, 532.03,
530.64, 524.10, 512.68, 512.61, 511.11, 506.87, 506.28, 492.95, 491.42,
490.95, 473.57, 467.41, 466.09, 462.90, 457.58, 452.83, 452.30, 451.00,
439.41, 438.69, 428.19, 427.73, 422.06, 396.39, 394.48, 393.00, 390.31,
382.23, 376.50, 375.48, 373.28, 372.49, 372.10, 360.18, 358.78, 358.72,
346.24, 345.51, 343.70, 329.57, 328.65, 327.80, 313.70, 312.93, 311.39,
310.88, 308.84, 301.57, 301.35, 299.36, 298.24, 298.20, 293.95, 276.15,
275.93, 250.24, 249.78, 248.11, 247.92, 247.84, 238.09, 237.73, 236.98,
200.83, 199.80, 199.60, 193.25, 192.88, 169.31, 164.03, 163.14, 162.86,
153.43, 151.92, 151.45, 150.86, 150.34, 147.78, 142.80, 134.43, 133.96,
131.26, 129.13, 121.85, 121.16, 119.91, 95.16, 82.15, 79.04, 73.33, 70.56,
55.15, 52.28, 51.09
3016.05, 2961.53, 1444.26, 1354.50, 1214.52, 1084.72, 1033.10, 900.34,
724.53, 720.70, 705.88, 702.32, 689.03, 680.54, 668.76, 658.34, 655.48,
648.33, 635.44, 619.09, 590.35, 581.57, 574.01, 556.49, 553.80, 547.80,
545.34, 535.71, 529.20, 518.54, 516.63, 512.47, 508.40, 499.66, 494.94,
490.47, 482.00, 475.30, 473.21, 470.38, 463.06, 458.47, 455.66, 452.61,
451.35, 438.03, 423.98, 418.97, 412.36, 409.02, 400.70, 389.97, 387.68,
385.70, 380.35, 378.20, 376.46, 370.53, 360.91, 356.09, 348.33, 345.96,
341.53, 337.95, 336.47, 328.94, 324.12, 321.88, 317.43, 311.76, 310.01,
307.58, 302.26, 296.35, 289.16, 285.67, 283.14, 273.65, 270.03, 265.01,
261.08, 258.00, 252.31, 250.19, 244.72, 239.93, 235.41, 230.66, 210.57,
205.77, 204.19, 199.68, 189.48, 184.31, 171.76, 170.64, 164.81, 162.35,
157.20, 151.50, 149.71, 148.60, 147.27, 144.57, 143.39, 136.23, 133.23,
128.32, 125.65, 115.84, 111.89, 110.16, 104.42, 90.60, 73.05, 68.33, 65.53
2983.38, 1524.61, 1361.38, 1310.72, 976.96, 746.18, 707.27, 704.31, 691.83,
684.99, 679.89, 673.63, 665.22, 656.28, 650.48, 638.45, 634.02, 615.68,
591.21, 584.84, 567.15, 558.01, 556.30, 549.12, 545.61, 535.84, 525.29,
518.98, 512.93, 509.49, 497.55, 492.64, 489.97, 478.46, 476.80, 472.80,
466.38, 461.61, 453.98, 448.42, 442.70, 435.59, 431.38, 426.34, 419.75,
407.45, 405.24, 396.56, 390.83, 388.90, 380.60, 374.78, 370.81, 364.68,
358.06, 357.87, 356.27, 345.03, 342.82, 336.00, 330.57, 327.63, 326.54,
316.58, 314.05, 307.58, 303.73, 300.93, 297.73, 289.58, 281.52, 277.72,
273.51, 271.27, 261.61, 259.23, 255.57, 248.70, 245.65, 243.03, 237.75,
233.49, 225.48, 207.70, 204.62, 201.51, 196.31, 186.84, 178.61, 173.66,
171.77, 171.12, 159.01, 157.07, 154.51, 148.65, 148.12, 146.69, 145.21,
138.95, 135.67, 130.93, 128.86, 121.16, 117.57, 110.14, 104.82, 101.11,
100.89, 95.81, 92.31, 74.76, 65.28, 58.99
2044.47, 757.40, 709.41, 703.95, 698.03, 687.57, 675.23, 666.39, 656.86,
648.25, 632.42, 621.94, 607.16, 599.38, 579.93, 566.34, 559.22, 548.12,
544.47, 536.92, 531.57, 521.03, 518.27, 512.28, 507.92, 498.64, 491.64,
S11
O*
CH3O*
CH3OH*
489.19,
434.95,
382.06,
344.41,
304.36,
261.34,
214.07,
159.71,
124.45,
51.64
487.17, 478.02, 476.89, 468.71, 464.18, 461.80, 452.47, 443.87,
431.15, 424.85, 416.99, 402.30, 398.81, 389.43, 386.86, 386.73,
377.19, 375.44, 369.82, 365.13, 363.01, 357.75, 352.95, 345.83,
338.05, 331.49, 329.75, 316.24, 314.70, 311.55, 306.73, 305.86,
299.88, 295.80, 293.69, 288.77, 284.15, 276.97, 275.23, 270.11,
255.49, 255.29, 251.11, 247.69, 240.14, 235.63, 231.36, 225.88,
208.17, 203.66, 192.07, 185.80, 181.41, 173.86, 169.76, 165.82,
156.06, 152.77, 152.18, 147.25, 145.99, 142.96, 134.84, 129.51,
115.46, 114.76, 112.47, 104.08, 101.59, 87.57, 72.95, 70.24, 67.52,
855.73,
666.33,
524.65,
481.63,
434.03,
380.31,
346.51,
309.65,
273.62,
206.66,
163.24,
133.96,
71.42
702.38, 702.16, 696.38, 692.48, 691.66, 687.41, 673.63, 667.26,
629.12, 607.26, 588.85, 555.24, 552.22, 550.70, 545.16, 528.15,
519.41, 510.71, 510.29, 508.51, 496.81, 494.06, 489.36, 484.42,
475.62, 469.70, 468.71, 466.34, 462.30, 447.15, 442.28, 435.55,
428.04, 419.18, 416.57, 406.43, 390.86, 389.60, 388.33, 386.14,
380.08, 376.87, 373.54, 371.17, 367.55, 357.26, 351.30, 350.87,
344.35, 344.27, 329.22, 325.68, 323.55, 312.66, 311.90, 310.41,
305.71, 303.07, 298.61, 296.24, 294.68, 290.34, 280.48, 278.56,
260.05, 252.76, 248.46, 246.66, 245.53, 243.72, 238.96, 233.94,
202.05, 200.94, 199.43, 197.01, 189.08, 174.70, 172.16, 170.63,
158.37, 156.27, 154.72, 153.19, 151.18, 150.37, 141.43, 134.26,
129.72, 128.36, 125.36, 124.02, 100.35, 90.39, 82.30, 77.02, 74.11,
2939.97, 2921.01, 2876.49, 1417.01, 1410.74, 1405.68, 1119.05, 1093.78,
1072.91, 698.77, 697.72, 690.19, 680.54, 677.16, 675.84, 666.95, 662.47,
662.36, 634.01, 610.02, 608.90, 553.17, 548.19, 547.73, 547.44, 533.39,
532.10, 526.93, 522.58, 504.95, 504.12, 501.77, 495.54, 493.98, 488.99,
487.42, 486.40, 480.29, 469.63, 464.43, 463.69, 451.35, 449.62, 449.22,
448.82, 440.00, 438.68, 426.14, 423.84, 422.27, 391.30, 390.11, 388.27,
385.55, 380.23, 373.96, 373.23, 372.50, 371.69, 370.30, 358.38, 357.28,
357.02, 343.40, 342.93, 341.20, 332.70, 332.23, 331.74, 319.05, 318.14,
312.49, 311.96, 310.98, 302.10, 301.95, 298.95, 297.87, 297.42, 294.26,
278.59, 277.33, 253.59, 249.02, 248.09, 245.98, 244.65, 240.70, 237.36,
235.55, 205.66, 201.88, 201.39, 199.43, 198.67, 193.32, 178.07, 171.77,
170.71, 168.68, 158.13, 157.41, 154.16, 153.56, 153.09, 149.96, 146.68,
138.49, 133.51, 131.25, 128.34, 125.65, 123.17, 113.20, 94.30, 92.80, 75.45,
73.96, 71.70, 70.27, 51.12
3519.13, 3093.22, 3057.64, 2983.02, 1459.09, 1441.85, 1419.17, 1319.70,
1142.22, 1071.55, 997.74, 718.23, 714.49, 702.99, 699.56, 685.65, 671.43,
668.91, 666.22, 659.15, 652.31, 650.77, 646.00, 636.20, 581.66, 567.81,
560.99, 560.06, 545.36, 542.99, 538.91, 535.29, 523.70, 521.47, 514.56,
513.03, 507.78, 506.46, 498.64, 491.04, 477.82, 476.34, 469.69, 467.58,
463.65, 461.36, 460.18, 455.50, 452.96, 451.47, 447.48, 436.65, 415.01,
399.34, 396.56, 394.74, 391.35, 386.91, 381.73, 378.17, 376.89, 372.78,
S12
369.62, 367.54, 364.91, 351.76, 345.69, 342.57, 337.98, 334.65, 334.18,
329.09, 325.74, 320.64, 319.66, 315.26, 313.50, 311.58, 303.06, 299.70,
296.35, 288.67, 281.69, 268.91, 267.85, 258.07, 257.42, 249.84, 248.88,
245.79, 245.45, 239.84, 238.18, 211.24, 206.71, 204.29, 197.54, 194.30,
184.21, 175.25, 170.49, 166.11, 163.96, 156.76, 154.75, 152.94, 150.97,
148.65, 145.78, 142.94, 138.29, 131.60, 129.85, 127.62, 123.16, 121.32,
112.92, 109.19, 96.34, 73.88, 69.76, 69.44, 68.174346, 64.241475, 32.598921
CH2O*
CHO*
CH2OH*
2967.35, 2822.94, 1641.96, 1476.80, 1257.66, 1169.50, 707.05, 705.12,
702.55, 699.69, 697.35, 695.95, 677.63, 670.30, 659.31, 644.22, 639.94,
628.24, 580.76, 563.92, 559.35, 558.87, 542.64, 539.73, 536.99, 530.24,
520.82, 518.56, 512.94, 510.66, 509.21, 504.01, 494.41, 491.19, 474.98,
468.19, 467.40, 465.29, 462.96, 456.74, 456.19, 451.98, 448.92, 448.02,
431.20, 429.12, 408.72, 398.11, 396.93, 391.71, 386.73, 381.28, 378.03,
377.63, 376.72, 372.51, 365.86, 364.02, 362.97, 346.44, 344.47, 343.48,
339.90, 338.25, 332.92, 327.44, 323.09, 320.82, 316.82, 314.65, 311.92,
309.44, 307.81, 300.75, 299.97, 294.11, 291.19, 285.61, 271.14, 270.07,
258.02, 255.00, 249.82, 248.71, 245.49, 241.60, 238.79, 235.84, 214.20,
208.46, 204.04, 202.76, 192.90, 190.88, 176.40, 168.31, 165.07, 162.69,
158.05, 153.33, 152.04, 149.61, 148.33, 145.97, 144.88, 140.86, 133.87,
130.57, 125.18, 121.90, 115.32, 111.01, 105.50, 96.41, 79.72, 74.82, 69.64,
64.37, 60.69, 44.44
2978.37, 1563.77, 1358.88, 1278.26, 992.56, 753.20, 716.70, 708.44, 704.27,
697.82, 694.30, 685.84, 678.63, 673.89, 649.71, 639.61, 635.25, 616.09,
589.67, 579.15, 555.54, 553.04, 546.38, 541.55, 531.90, 526.54, 519.23,
512.75, 510.99, 503.60, 498.68, 484.91, 484.05, 481.73, 476.55, 470.34,
468.17, 460.34, 456.62, 454.27, 449.48, 446.55, 429.60, 425.86, 418.73,
405.73, 399.88, 398.96, 393.79, 387.76, 381.89, 379.21, 377.42, 372.74,
369.30, 364.54, 356.56, 348.87, 346.61, 345.49, 342.38, 334.88, 332.80,
328.42, 320.09, 318.61, 316.35, 310.68, 307.81, 303.23, 298.76, 294.16,
291.86, 282.07, 276.65, 272.20, 267.08, 264.07, 260.56, 255.99, 253.55,
246.80, 244.22, 241.60, 239.47, 233.97, 226.25, 214.97, 210.66, 205.51,
195.60, 193.30, 185.77, 182.56, 177.12, 167.12, 162.16, 159.44, 158.13,
152.07, 150.20, 147.95, 146.28, 144.80, 137.22, 136.55, 131.41, 125.26,
123.32, 120.49, 111.55, 103.89, 91.82, 78.77, 77.47, 63.28, 52.79
3494.64, 3010.78, 2933.49, 1458.25, 1375.44, 1332.55, 1222.49, 1080.39,
1041.78, 875.37, 712.26, 707.08, 702.24, 697.57, 695.12, 684.35, 672.11,
669.50, 664.21, 659.04, 643.63, 640.00, 609.45, 573.29, 565.24, 556.02,
551.26, 548.90, 546.14, 536.94, 529.79, 526.69, 518.79, 515.12, 513.34,
506.85, 503.77, 495.71, 483.79, 478.77, 476.65, 473.35, 468.76, 463.78,
457.51, 456.56, 444.17, 442.17, 432.53, 424.67, 409.08, 401.90, 395.99,
394.30, 390.84, 386.43, 381.84, 380.09, 375.10, 372.05, 369.97, 361.53,
360.52, 348.17, 346.68, 344.56, 342.02, 338.23, 333.26, 326.71, 322.48,
318.61, 316.67, 311.24, 308.74, 304.30, 303.03, 297.52, 297.04, 294.70,
288.94, 282.28, 270.53, 261.03, 257.15, 251.74, 249.92, 248.82, 245.98,
S13
240.35, 238.89, 233.64, 208.15, 204.71, 200.88, 200.07, 198.38, 192.62,
184.58, 175.29, 172.22, 165.66, 161.38, 157.14, 154.85, 152.80, 147.85,
144.83, 142.30, 139.69, 135.59, 131.37, 128.13, 123.53, 116.34, 113.00,
109.34, 94.74, 83.60, 70.31, 65.18, 58.84, 43.75
CHOH*
OH*
H2O*
TS
3500.09, 2908.80, 1410.93, 1282.37, 1171.11, 879.95, 696.27,
694.86, 691.25, 689.93, 685.31, 676.00, 671.92, 671.56, 666.17,
644.52, 567.67, 559.21, 559.01, 558.37, 538.37, 536.77, 534.65,
514.66, 512.90, 512.62, 508.11, 506.83, 495.68, 493.82, 493.38,
468.43, 467.50, 459.88, 458.69, 457.34, 453.73, 447.10, 446.15,
433.97, 432.53, 426.08, 411.39, 397.85, 394.38, 394.02, 390.66,
376.53, 375.28, 373.12, 371.78, 370.07, 364.39, 361.28, 358.64,
343.52, 342.06, 335.11, 333.13, 329.27, 320.56, 317.15, 316.07,
306.99, 305.15, 304.65, 303.73, 297.44, 296.55, 292.49, 273.15,
258.04, 252.80, 252.49, 248.05, 245.73, 243.08, 241.45, 238.25,
203.93, 203.28, 202.45, 196.60, 194.89, 174.03, 166.68, 165.70,
154.57, 153.55, 152.75, 149.93, 148.86, 147.43, 143.48, 132.65,
130.15, 124.05, 123.31, 116.66, 108.26, 72.72, 71.93, 45.84, 25.06
695.62,
648.89,
528.05,
474.39,
434.23,
385.72,
344.93,
315.24,
273.00,
224.00,
164.08,
131.95,
3767.52, 698.66, 698.00, 691.27, 676.05, 673.51, 671.93, 664.26, 660.07,
658.78, 641.94, 622.01, 603.28, 600.69, 576.60, 550.93, 546.19, 545.24,
544.77, 533.27, 531.91, 525.10, 522.38, 503.27, 502.20, 498.80, 492.18,
491.36, 486.68, 485.07, 484.64, 469.79, 463.88, 463.31, 451.75, 449.47,
448.24, 447.36, 440.59, 439.44, 429.63, 422.98, 422.11, 390.28, 387.87,
386.47, 384.41, 379.20, 374.32, 372.41, 372.25, 370.78, 368.99, 357.16,
356.19, 355.08, 342.01, 341.12, 339.33, 333.48, 332.12, 331.98, 318.88,
318.03, 312.28, 311.50, 310.04, 302.52, 301.17, 299.44, 297.78, 297.23,
295.22, 278.30, 277.39, 252.53, 248.38, 247.74, 245.71, 244.39, 241.54,
237.67, 236.44, 203.25, 202.65, 202.24, 200.73, 200.34, 185.52, 173.54,
172.33, 172.22, 160.26, 158.74, 156.70, 155.43, 155.08, 153.98, 150.61,
141.98, 137.86, 133.15, 129.45, 128.27, 124.67, 118.64, 101.33, 96.39, 86.24,
80.87, 78.37, 72.38, 62.04
3731.56, 2816.94, 1604.26, 1001.89, 717.97, 708.35, 705.28, 702.66, 699.35,
695.93, 678.13, 667.87, 661.36, 648.68, 641.41, 631.81, 611.42, 583.00,
564.66, 560.56, 557.17, 543.43, 539.92, 538.66, 530.82, 519.52, 515.48,
513.18, 510.18, 508.81, 502.23, 494.48, 492.21, 476.08, 469.88, 469.14,
466.52, 460.21, 459.04, 456.39, 452.78, 449.03, 448.18, 436.91, 430.42,
428.57, 408.70, 398.47, 396.72, 391.68, 389.26, 383.23, 379.91, 377.99,
375.41, 372.12, 363.91, 361.74, 357.49, 349.69, 343.45, 340.41, 338.47,
336.55, 328.05, 324.17, 320.69, 319.30, 315.86, 311.86, 310.36, 300.98,
299.96, 297.23, 291.17, 289.14, 286.90, 271.48, 266.50, 257.50, 254.10,
248.89, 248.35, 244.39, 240.67, 237.20, 233.97, 213.62, 208.79, 202.69,
195.78, 192.56, 188.54, 172.63, 169.72, 165.44, 164.40, 157.33, 155.59,
153.13, 151.65, 148.68, 147.14, 142.98, 141.23, 130.36, 129.63, 125.52,
123.05, 119.42, 117.46, 105.01, 91.27, 78.36, 69.58, 69.08, 64.84
-1302.10, 3084.82, 3026.19, 2928.51, 1744.18, 1414.42, 1405.24, 1148.56,
S14
CH4* CH3* + H*
1103.96, 715.45, 710.12, 708.19, 704.23, 700.04,
670.51, 653.81, 650.89, 646.15, 620.13, 582.04,
550.29, 544.67, 539.48, 538.46, 526.94, 522.32,
509.03, 505.08, 494.69, 491.31, 476.86, 472.31,
461.04, 454.42, 452.38, 449.72, 444.25, 439.17,
397.49, 394.12, 392.36, 383.65, 381.73, 379.48,
367.95, 363.96, 360.04, 346.29, 343.67, 343.42,
324.20, 320.45, 317.12, 314.08, 312.39, 309.39,
293.97, 293.39, 278.12, 272.37, 270.18, 253.91,
245.33, 238.57, 235.57, 209.80, 206.55, 203.77,
170.39, 168.19, 165.69, 162.49, 154.30, 153.25,
146.59, 143.92, 134.72, 128.79, 124.96, 118.51,
96.90, 84.38, 77.21, 71.19, 69.92, 65.18
695.25,
563.88,
521.43,
469.54,
429.77,
378.20,
339.06,
306.75,
252.38,
200.67,
152.12,
117.93,
681.53,
562.10,
512.50,
467.20,
413.88,
377.15,
338.04,
302.13,
247.97,
193.64,
151.11,
116.71,
675.60,
560.46,
510.32,
462.36,
407.98,
370.98,
328.16,
299.57,
246.16,
185.00,
148.16,
108.04,
TS
CH4* + O* CH3OH*
-783.57, 3135.74, 3131.12, 3001.33, 1388.88, 1387.73, 1197.28, 1126.01,
1103.48, 847.97, 699.80, 699.52, 691.76, 678.56, 676.80, 675.36, 666.68,
662.03, 661.21, 619.92, 599.49, 597.20, 551.80, 546.48, 545.23, 544.81,
532.36, 531.08, 524.42, 522.36, 504.23, 503.89, 500.42, 493.07, 491.09,
487.37, 486.39, 485.15, 469.55, 465.25, 463.38, 452.32, 450.36, 449.46,
447.97, 442.00, 439.15, 438.90, 424.00, 422.67, 419.96, 393.28, 389.78,
388.98, 387.35, 383.98, 379.39, 373.93, 373.55, 373.52, 372.49, 369.33,
358.25, 357.97, 356.50, 356.13, 342.86, 342.49, 340.79, 333.26, 332.23,
332.02, 318.74, 318.45, 312.53, 312.23, 310.84, 303.03, 302.65, 299.91,
298.37, 297.50, 293.37, 278.70, 278.42, 251.51, 249.02, 248.57, 245.41,
245.00, 242.94, 237.47, 235.96, 202.76, 202.07, 201.58, 200.41, 200.00,
183.13, 172.79, 172.77, 171.84, 160.40, 158.83, 158.40, 155.09, 154.31,
153.72, 150.29, 140.30, 139.37, 133.27, 129.64, 129.16, 124.06, 114.99,
98.14, 90.60, 81.58, 80.14, 73.39, 72.76, 65.03, 51.56, 37.22
TS
CH3* CH2* + H*
-1716.68, 3075.78, 2883.53, 1441.83, 1396.19, 1191.54, 1156.94, 1097.60,
1020.55, 720.46, 714.46, 710.87, 690.02, 685.85, 680.81, 668.80, 653.86,
649.61, 643.60, 610.29, 586.70, 584.17, 573.03, 571.44, 565.13, 560.72,
550.98, 544.83, 541.57, 532.41, 529.08, 520.80, 517.62, 510.63, 505.43,
504.70, 491.41, 484.57, 481.37, 480.43, 472.38, 470.98, 465.79, 462.90,
455.67, 451.06, 443.39, 440.44, 424.25, 414.88, 406.70, 399.86, 398.04,
389.62, 387.67, 383.78, 379.13, 376.73, 373.83, 369.44, 365.44, 364.00,
358.91, 348.51, 347.19, 340.48, 337.41, 334.92, 330.47, 326.42, 321.33,
317.38, 314.07, 307.92, 304.93, 301.95, 297.55, 292.97, 288.10, 279.39,
273.05, 266.68, 259.77, 254.69, 251.78, 246.63, 242.02, 240.10, 238.10,
228.12, 227.00, 210.32, 203.57, 201.35, 191.22, 183.31, 177.60, 168.74,
166.11, 161.94, 155.15, 153.96, 152.76, 151.52, 145.50, 142.04, 135.83,
132.25, 130.44, 122.70, 117.52, 113.13, 109.90, 104.75, 97.29, 95.93, 89.58,
82.82, 69.03, 64.89
TS
CH2O* CHO* + H*
-137.01, 2767.12, 2642.25, 1418.71, 1255.11, 1014.92, 904.90, 707.02,
704.08, 702.34, 699.68, 695.81, 691.74, 687.00, 679.35, 674.22, 671.20,
660.42, 577.74, 565.00, 563.12, 558.86, 548.92, 540.52, 536.92, 531.99,
S15
523.87, 523.57, 516.95, 514.70, 511.85, 507.03, 499.04, 494.54, 488.26,
486.77, 475.53, 472.68, 469.15, 465.97, 456.37, 455.72, 447.41, 442.64,
435.81, 429.72, 426.43, 413.39, 405.63, 396.15, 394.71, 391.58, 387.71,
381.90, 379.90, 375.47, 375.39, 373.73, 371.48, 361.67, 359.19, 353.92,
348.12, 345.01, 342.45, 332.11, 328.77, 324.68, 317.82, 315.41, 311.29,
310.10, 307.52, 305.06, 302.39, 302.07, 296.32, 295.97, 292.77, 279.26,
275.49, 254.78, 252.31, 250.42, 247.13, 245.91, 242.45, 238.26, 236.95,
205.45, 202.51, 201.17, 197.27, 194.47, 181.06, 172.61, 170.28, 167.11,
166.19, 158.50, 156.10, 155.02, 152.18, 150.36, 147.93, 145.73, 144.09,
134.08, 131.93, 127.75, 122.72, 122.20, 119.36, 106.74, 94.89, 76.50, 72.09,
71.08, 51.74, 38.01
TS
CO* + O (lattice) CO2* (VO)
-296.66, 1849.60, 709.33, 705.44, 703.50, 701.93, 699.00,
675.82, 674.40, 667.18, 662.99, 621.10, 582.29, 563.57,
542.37, 536.67, 535.87, 527.19, 520.25, 514.90, 512.90,
495.12, 494.25, 486.89, 485.39, 472.52, 470.35, 468.18,
451.37, 447.61, 438.64, 433.33, 427.36, 424.28, 414.77,
391.55, 388.34, 383.85, 380.42, 378.28, 376.20, 374.98,
360.04, 354.36, 347.81, 346.34, 343.21, 338.43, 331.21,
314.98, 313.14, 310.98, 310.21, 308.76, 306.23, 303.27,
295.77, 287.97, 281.19, 276.88, 267.50, 252.45, 250.53,
241.54, 237.68, 236.96, 207.19, 201.77, 200.51, 199.21,
171.33, 170.85, 168.89, 161.46, 157.79, 155.63, 154.46,
148.17, 143.98, 135.01, 132.82, 129.44, 125.09, 121.32,
96.54, 82.75, 77.12, 72.18, 69.90, 65.85
TS
2H* + O (lattice) H2O* (VO)
-1043.17, 1585.80, 1278.49, 790.00, 735.44, 717.77, 710.00, 699.75, 690.93,
681.40, 677.12, 662.72, 640.59, 637.26, 601.73, 591.54, 576.27, 573.36,
564.59, 554.73, 550.38, 544.73, 539.78, 529.38, 523.60, 518.12, 510.15,
506.47, 505.65, 495.18, 489.38, 478.73, 475.40, 475.12, 468.19, 459.50,
457.93, 456.38, 450.62, 445.84, 443.63, 431.07, 420.39, 419.34, 405.08,
397.53, 393.09, 387.90, 386.88, 384.76, 379.49, 374.01, 372.43, 366.03,
361.31, 358.94, 351.21, 347.33, 343.17, 338.77, 336.98, 332.20, 330.21,
326.52, 320.47, 317.77, 311.75, 308.86, 307.57, 304.47, 295.04, 291.29,
282.00, 276.74, 263.11, 258.09, 250.40, 248.30, 247.14, 242.27, 237.07,
231.82, 213.79, 204.98, 203.85, 201.64, 192.80, 180.33, 171.93, 171.18,
164.01, 158.75, 154.90, 154.71, 150.01, 147.70, 142.55, 141.51, 138.83,
132.04, 129.14, 122.09, 118.63, 114.73, 110.83, 98.00, 93.23, 78.39, 69.25
TS
OH* + H* H2O*
-404.23, 3750.77, 1424.12, 1330.08, 906.47, 724.10, 717.33, 715.22, 713.76,
706.38, 703.99, 700.38, 679.21, 669.56, 662.88, 647.94, 638.60, 611.01,
594.44, 570.04, 568.14, 557.96, 551.00, 548.87, 543.80, 534.91, 523.49,
517.55, 514.47, 512.50, 508.98, 506.15, 501.87, 494.64, 492.31, 480.73,
477.61, 474.52, 472.06, 464.64, 459.25, 457.20, 454.09, 448.11, 440.46,
435.40, 426.97, 415.61, 410.40, 402.24, 399.98, 393.87, 390.66, 385.71,
382.87, 379.61, 376.95, 375.92, 364.25, 360.10, 353.63, 352.78, 347.93,
342.67, 339.10, 333.75, 331.61, 324.43, 320.09, 319.12, 313.69, 312.88,
694.12,
561.35,
510.53,
467.56,
398.87,
373.20,
329.47,
301.04,
248.47,
195.32,
152.02,
113.69,
687.23,
556.87,
509.63,
452.82,
395.40,
362.26,
320.05,
299.79,
246.28,
187.45,
149.88,
109.46,
S16
TS
CH3* + O* CH3O*
309.68, 300.60, 297.99, 295.15, 292.66, 281.04, 268.49, 265.97,
254.80, 251.39, 248.56, 247.19, 240.43, 235.61, 232.48, 209.99,
201.68, 197.29, 189.75, 187.31, 177.19, 170.76, 165.88, 163.84,
158.69, 157.09, 152.58, 149.34, 147.39, 146.09, 137.76, 130.68,
125.82, 122.66, 122.12, 103.19, 100.44, 89.71, 85.38, 69.68, 67.40
259.93,
204.84,
161.46,
127.65,
-595.42, 3242.97, 3191.78, 3040.57, 1422.12, 1358.08, 1142.95,
768.89, 727.45, 716.96, 712.59, 707.11, 702.05, 696.88, 676.85,
658.70, 648.30, 639.96, 631.54, 601.94, 582.96, 564.93, 562.34,
542.24, 539.97, 535.10, 531.36, 523.60, 518.42, 512.59, 505.91,
495.55, 491.48, 486.85, 477.74, 470.34, 469.35, 467.51, 464.30,
455.79, 451.92, 447.87, 441.20, 427.83, 413.86, 402.41, 398.65,
390.41, 385.70, 385.05, 380.16, 378.78, 378.23, 373.90, 368.29,
362.41, 353.40, 348.66, 345.79, 343.79, 341.17, 339.52, 326.30,
318.84, 316.07, 314.41, 310.08, 308.84, 302.28, 300.46, 294.37,
278.72, 272.72, 264.88, 261.17, 260.54, 255.56, 251.22, 247.80,
244.33, 235.10, 210.85, 207.26, 205.07, 202.09, 195.70, 191.45,
174.73, 172.31, 168.63, 166.84, 162.71, 157.31, 153.38, 153.07,
147.88, 147.76, 141.19, 131.54, 128.47, 124.82, 123.04, 121.97,
108.54, 106.10, 101.83, 96.48, 89.85, 69.38, 68.87
854.85,
669.66,
559.28,
504.39,
461.43,
394.80,
364.97,
321.89,
290.32,
245.72,
187.41,
151.39,
118.41,
TS
CH3O* + H* CH3OH*
-978.34, 3014.83, 2998.94, 2935.21, 1733.10, 1451.20, 1441.41, 1418.57,
1276.04, 1144.16, 1124.60, 1059.15, 717.98, 709.82, 706.48, 703.91, 701.60,
693.15, 677.31, 672.94, 665.02, 653.57, 650.40, 647.41, 582.93, 564.46,
561.94, 560.94, 555.45, 541.52, 538.46, 531.01, 523.74, 521.35, 513.38,
513.12, 509.34, 505.45, 495.55, 492.27, 476.93, 473.00, 469.45, 468.76,
463.07, 461.32, 456.70, 452.21, 449.54, 446.29, 442.91, 430.61, 422.65,
417.83, 406.61, 396.66, 395.21, 392.13, 383.71, 379.47, 379.03, 377.44,
377.16, 369.34, 364.35, 360.65, 352.98, 344.25, 342.93, 340.17, 337.39,
335.86, 324.35, 320.68, 318.96, 315.47, 311.33, 309.57, 308.38, 302.18,
300.01, 298.38, 293.11, 284.06, 272.22, 271.28, 255.85, 252.34, 248.58,
246.84, 246.26, 239.56, 235.93, 217.04, 208.65, 207.86, 203.54, 198.78,
196.52, 184.96, 175.32, 169.97, 166.24, 162.85, 157.10, 154.46, 152.78,
150.17, 149.30, 148.43, 142.88, 132.76, 129.60, 127.66, 126.16, 120.09,
117.74, 115.73, 100.23, 92.99, 82.54, 73.35, 73.07, 68.15, 44.36
TS
CH2OH* CHOH* +
H*
-1266.04, 3699.85, 3078.10, 2994.69, 1716.36, 1401.29, 1272.13, 1177.36,
1097.48, 1011.85, 823.78, 708.10, 706.36, 703.50, 700.29, 696.90, 693.05,
677.85, 666.42, 650.92, 649.19, 643.69, 616.88, 579.06, 564.18, 561.32,
560.56, 556.42, 545.60, 539.54, 538.67, 530.52, 521.36, 521.15, 511.88,
509.55, 507.89, 504.70, 493.67, 491.75, 476.06, 470.35, 468.18, 467.29,
462.36, 459.73, 456.16, 453.28, 449.67, 448.76, 440.44, 430.22, 413.08,
409.53, 405.09, 396.89, 394.08, 393.06, 383.05, 379.84, 376.93, 375.45,
374.88, 368.71, 368.10, 362.51, 355.93, 346.19, 342.70, 341.95, 338.42,
335.74, 329.86, 325.27, 319.15, 318.43, 314.69, 311.68, 309.46, 305.47,
300.81, 297.64, 295.79, 293.33, 284.23, 281.82, 271.22, 270.48, 253.31,
252.25, 247.92, 244.62, 243.58, 238.78, 233.46, 210.44, 206.44, 203.63,
S17
199.92, 193.61, 183.01, 170.48, 167.28, 165.19, 160.70, 154.74, 151.97,
150.54, 149.68, 148.53, 145.37, 141.30, 134.06, 129.18, 125.21, 119.65,
117.58, 116.25, 92.26, 86.33, 76.24, 75.04, 70.61, 66.09, 64.56, 46.36
S18
6. References
1.
Reuter, K.; Scheffler, M., Composition, Structure, and Stability of Ruo2(110)$ as a Function of Oxygen
Pressure. Phys. Rev. B 2001, 65, 035406.
2.
Reuter, K.; Scheffler, M., First-Principles Atomistic Thermodynamics for Oxidation Catalysis: Surface
Phase Diagrams and Catalytically Interesting Regions. Phys Rev Lett 2003, 90, 046103.
3.
Meyer, B.; Marx, D., Density-Functional Study of the Structure and Stability of Zno Surfaces. Phys. Rev. B
2003, 67, 035403.
4.
Warschkow, O.; Chuasiripattana, K.; Lyle, M. J.; Delley, B.; Stampfl, C., Cu/Zno(0001) under Oxidating
and Reducing Conditions: A First-Principles Survey of Surface Structures. Phys. Rev. B 2011, 84, 125311.
5.
Tang, J.-J.; Yang, X.-B.; Chen, M.; Zhu, M.; Zhao, Y.-J., First-Principles Study of Biaxial Strain Effect on
Hydrogen Adsorbed Mg (0001) Surface. J. Phys. Chem. C 2012, 116, 14943-14949.
6.
Kiejna, A.; Pabisiak, T., Surface Properties of Clean and Au or Pd Covered Hematite (Α-Fe2o3) (0001). J.
Phys.: Conden. Matt. 2012, 24, 095003.
7.
Wang, X. G.; Weiss, W.; Shaikhutdinov, S.; Ritter, M.; Petersen, M.; Wagner, F.; Schlögl, R.; Scheffler, M.,
The Hematite Α-Fe2o3 (0001) Surface: Evidence for Domains of Distinct Chemistry. Phys Rev Lett 1998, 81,
1038-1041.
8.
Rohrbach, A.; Hafner, J.; Kresse, G., Ab Initio Study of the (0001) Surfaces of Hematite and Chromia:
Influence of Strong Electronic Correlations. Phys. Rev. B 2004, 70, 125426.
9.
Maike, L.; Wolfgang, M., A Leed Analysis of the Clean Surfaces of Α-Fe 2 O 3 (0001) and Α-Cr 2 O 3
(0001) Bulk Single Crystals. Journal of Physics: Condensed Matter 2009, 21, 134010.
10. Barbier, A.; Stierle, A.; Kasper, N.; Guittet, M. J.; Jupille, J., Surface Termination of Hematite at
Environmental Oxygen Pressures: Experimental Surface Phase Diagram. Phys. Rev. B 2007, 75, 233406.
11. Maike, L.; Wolfgang, M., A Leed Analysis of the Clean Surfaces of Α-Fe2o3 (0001) and Α-Cr2o3 (0001)
Bulk Single Crystals. Journal of Physics: Condensed Matter 2009, 21, 134010.
12. Pabisiak, T.; Kiejna, A., Fe Adsorption on Hematite (Α-Fe2o3) (0001) and Magnetite (Fe3o4) (111) Surfaces.
J. Chem. Phys. 2014, 141, 134707
13. Liu, B.; Greeley, J., Decomposition Pathways of Glycerol Via C–H, O–H, and C–C Bond Scission on
Pt(111): A Density Functional Theory Study. J. Phys. Chem. C 2011, 115, 19702-19709.
14. Liu, B.; Cheng, L.; Curtiss, L.; Greeley, J., Effects of Van Der Waals Density Functional Corrections on
Trends in Furfural Adsorption and Hydrogenation on Close-Packed Transition Metal Surfaces. Surf Sci 2014,
622, 51-59.
15. Nørskov, J. K., et al., Universality in Heterogeneous Catalysis. J Catal 2002, 209, 275-278.
S19