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Caption : fig. s1 (a) xrd patterns of the as-prepared catalyst.

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Caption : fig. s2 haadf-stem images of 0.2feox/tio2.

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Caption : fig. s3 (a) k3-weighted fourier-transform fe k-edge extended x-ray absorption fine structure exafs spectra in r space for 0.2feox/tio2 in reference to fe foil, feo, fe3o4, fe2o3 and feooh; (b) exafs fitting curve for 0.2feox/tio2 in r space.

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Caption : fig. s4 (a) schematic diagram and (b) setup of the flow reactor system for photocatalytic nocm reaction.

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Caption : fig. s5 calibration curves for the quantification of (a) c2h6, (b) c3h8, (c) co2, and (d) co.

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Caption : fig. s6 nocm reaction over tio2 and tio2 supported with different amounts of feox under (a) 15 ml/min-1 and (b) 10 ml/min-1 of ch4 feed flow rate. reaction conditions: 20 mg catalyst, 25 °c reaction temperature, 300 w xe lamp, wavelength range 200~1300 nm, light intensity 600 mw cm-2.

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Caption : fig. s7 control experiments for nocm reaction over 0.2feox/tio2 or in the absence of catalyst, light irradiation or ch4. (reaction conditions in presence of 0.2feox/tio2: 20 mg catalyst, 10 ml min-1 of ch4, 25 °c reaction temperature, 300 w xe lamp, wavelength range 200~1300 nm, light intensity 600 mw cm-2. other control experiments were conducted under the above conditions, except that the absence of catalyst, light irradiation or ch4.) 

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Caption : fig. s8 mass spectra of c2h6 produced over 0.2feox/tio2 using 13ch4 and 12ch4 as a reactant, respectively.

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Caption : fig. s9 xrd patterns of fresh and spent 0.2feox/tio2 catalyst.

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Caption : fig. s10 haadf-stem images of (a) fresh and (b) spent 0.2feox/tio2 catalyst.

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Caption : fig. s11 room-temperature epr spectra of (a) fresh and (b) spent 0.2feox/tio2 catalyst.

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Caption : fig. s12 (a) bandgap of the samples determined from the tauc plots; (b-d) mott-schottky plots.

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Caption : fig. s13 (a) transient photocurrent density, and (b) electrochemical impedance spectra of the samples.

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Caption : fig. s14 online mass spectra of h2o product in nocm reaction over 0.2feox/tio2.

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Caption : fig. s15 the optimized structural models of (a) tio2 and (b) 0.2feox/tio2.

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Caption : fig. s16 optimized configurations. (a) ch4, (b) *ch3, (c) *2ch3, and (d) *ch3-ch3 intermediates on tio2. (e) ch4, (f) *ch3, (g) *2ch3, and (h) *ch3-ch3 intermediates on 0.2feox/tio2.

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Caption : fig. s17 transition states formed by the interaction between *ch3 and lattice oxygen for (a) tio2 and (b) 0.2feox/tio2.

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Caption : fig. s18 in situ epr spectra of 0.2feox/tio2 in the dark and under light irradiation.