Revealing *OOH key intermediates and regulating H2O2

photoactivation by surface relaxation of Fenton-like catalysts

Xiaoming Xua,b, Yuanming Zhanga,b, Yong Chena,b, Changhao Liua,b, Wenjing Wanga,b, Jiajia Wangc,
Huiting Huanga,b, Jianyong Fenga,b, Zhaosheng Li a,b,1, and Zhigang Zoua,b

Zhaosheng Li
Email: zsli@nju.edu.cn.

This PDF file includes:

Supplementary text
Figures S1 to S25 (not allowed for Brief Reports)
Tables S1 to S3 (not allowed for Brief Reports)

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 Fe(NO3) 3·9H2O Ti-doped YFO Precursor
Y(NO3) 3·6H2O 730 °C
C6H8O7·H2O
C6H18N2O8Ti Annealing

After 450 °C
grinding Decarbonizing

Fully stirring
Oil bath
Heating stage Evaporating water
Magnetic rotation 120 °C
Drying in the oven

Fig. S1. Schematic illustration of the preparation process of YFeO3.

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Fig. S2. XRD patterns of YFeO3 after the treatment at different temperatures.

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Fig. S3. XRD patterns of YFeO3 with different Ti doped ratios.

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Fig. S4. (a) Light harvesting efficiency spectra for YFeO3 with different Ti doped ratios. (b)
Electrochemical impedance spectra (EIS) of pure YFeO3, 3%, 5% and 7% Ti-doped YFeO3 in a 1
M NaOH electrolyte at 1.6 V vs RHE. The right inset is an equal circuit for the catalyst/electrolyte
interfaces. Electrochemical impedance spectrum fitting result is shown in Table S3. Rs is the
electrolyte resistance. Rct and CPE is the charge-transfer resistance from the bulk to the surface of
catalyst and the constant phase element, respectively.

Fig. S4 showed the photo-absorption curve of pure YFeO3, 3%, 5% and 7% Ti-doped YFeO3.
YFeO3 showed good light harvest and absorption capacity1. The cutoff wavelength of YFeO3
could reach about 700 nm.

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Fig. S5. XPS survey spectra. (a) XPS survey spectra of pure YFeO3 and 3% Ti-doped YFeO3
from 0 to 1000 eV. XPS spectra of pure YFeO3 and 3% Ti-doped YFeO3: (b) Ti 2p, (c) Y 3d, (d) O
1s

Fig. S5a showed the XPS survey spectra of pure YFeO3 and 3% Ti-doped YFeO3 from 0 to 1000
eV. Fig. S5c showed the high-resolution Y 3d region with two spin-orbit doublets with the main
peaks. The Ti 2p region XPS spectra of pure YFeO3 and 3% Ti-doped YFeO3 were distinguished
by Fig. S5b. There were two signals in the spectra of 3% Ti-doped YFeO3 located at 458.2 eV and
464.3 eV corresponding to Ti 2p3/2 and Ti 2p1/2, which was agreed with the reported date2. It
meant the doped Ti ions were presented as Ti4+ species. Fig. S5d showed the O 1s XPS spectra.
At lower binding energy represent the oxygen in lattice and the surface absorbed oxygen observed
at higher binding energy. The shift of O 1s peak to higher energy after Ti doping again proved that
Ti element successfully entered the lattice of YFeO3.

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 Y Fe O Ti
a1 a2 a3 a4 a5 a6

Y Fe O Ti 10 μm

b1 b2 b3 b4 b5 b6

Y Fe O Ti
10 μm

c1 c2 c3 c4 c5 c6

Y Fe O Ti 10 μm

d1 d2 d3 d4 d5 d6

Y Fe O Ti 10 μm

Fig. S6. SEM and EDS images. (a) YFeO3, (b) 3% Ti-doped YFeO3, (c) 5% Ti-doped YFeO3, (d)
7% Ti-doped YFeO3.

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Fig. S7. TEM images. Low-resolution TEM of (a) YFeO3, (d) 3% Ti-doped YFeO3. In the high-
resolution TEM images, the lattice spacings of (b) YFeO3, (e) 3% Ti-doped YFeO3 are visible.
Electron diffraction spot of (c) YFeO3, (f) 3% Ti-doped YFeO3

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 a 3% Ti-doped YFO

Pure YFO

b 3% Ti-doped YFO c
3% Ti-
doped YFO

Pure YFO Pure YFO

Fig. S8. The specific surface area and pore size distributions of the samples. (a) Nitrogen
adsorption-desorption isotherms. (b) Pore size distribution based on BJH model. (c) The BET
surface areas of pure and 3% Ti-doped YFeO3.

The specific surface area and pore size distributions of the samples were measured using the
BET method. As noted in Supplementary Fig. 8a the isotherms were classified as type IV with H2
hysteresis loops (0.5–1 P/P0) according to the International Union of Pure and Applied Chemistry
(IUPAC) classification and the specific surface area of 3% Ti-doped YFeO3 reached 18.38 m2g-1,
similarly to that of pure YFeO3 (16.81 m2g-1) (Fig. S8c).

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Fig. S9. Spherical aberration-corrected scanning transmission electron (STEM) images. (a, b)
annular bright field (ABF) image of pure YFeO3 and Ti-YFeO3 and (c) high-angel annular dark field
(HADDF) image of Ti-YFeO3. (The right is the selected area of the left.) The scale bars are 1nm.
(d) The corresponding fast Fourier transform (FFT) patterns of Ti-YFeO3. (e) The crystal structure
model of (001) plane and (f) perpendicular to the (001) plane. (g) Profile of the line in (c). The yellow
and blue spheres represent Fe and Y atoms.

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Fig. S10. Shell-isolated nanoparticle-enhanced Raman spectroscopy of H2O2 (3 wt.% H2O2/H2O)
and H218O2 (18O isotope labelling, 2-3 wt.% H218O2/H2O).

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 a b

c d

Fig. S11. Photo-Fenton reaction performance. (a) Time dependent RhB solution degradation in
different systems. Specially, in pure YFeO3 light and 3% Ti-doped YFeO3 light systems, there were
no H2O2. (b) Time dependent RhB solution degradation for pure YFeO3 and 3%, 5%, 7% Ti-doped
YFeO3 with H2O2. (c, d) the corresponding Langmuir-Hinshelwood kinetics plots in these systems.

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Fig. S12. UV–vis spectral changes for RhB degradation with Ti-YFeO3/H2O2/light system.

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Fig. S13. The removal efficiencies of different pollutants after reacting for 3 h.

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 5 mg L −1 3 mg L −1 1 mg L −1

0.7 mg L −1 0.5 mg L −1 0.3 mg L −1

0.1 mg L −1 0.05 mg L −1 0 mg L −1

Fig. S14. Calibration curve of 4-CP for 3-dimension excitation emission matrix fluorescence
spectroscopy (3D-EEM). The left part showed 3D-EEM of 4-CP aqueous solutions with different
concentrations (0 to 5 mg L−1). The excitation range was 270 to 340 nm, and the emission range
was 290 to 450 nm. The right part showed that 3D-EEM intensity of 4-CP aqueous solutions had a
linear relationship with the concentrations.

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Fig. S15. Calibration curve under 4-aminoantipyrine methods. The left part showed the light
absorption curves of 4-CP solutions with different concentrations (0 to 3 mg L−1) under the test of
4-aminoantipyrine methods. The right part showed that light absorption intensity of 4-CP aqueous
solutions had a linear relationship with the concentrations.

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Fig. S16. 3D-EEM fluorescence spectra of 4-CP after different time degradation. (From left to right:
0 min, 30min, 90min, 180min.)

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Fig. S17. Degradation efficiencies of RhB in Ti-YFeO3/H2O2 light system with 3-round reactions.

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 a b c

Fig. S18. Calibration curves of Fe3+ ions under the 1, 10-phenanthroline method and detection
curves of Fe3+ ions for the different systems. (a) The light absorption curves with different-
concentration Fe3+ ions under the test of 1, 10-phenanthroline methods. (b) The light absorption
intensity had a linear relationship with the concentrations. (c) Absorptance curves of Fe3+ ions in
the solution after reaction for pure YFeO3 and Ti-YFeO3 under the 1, 10-phenanthroline method.

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 a

Fig. S19. Characterization of catalysts before and after reaction. (a) Fourier translation infrared
spectroscopy (FT-IR) and (b) XRD of Ti-YFeO3 before and after reaction.

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Fig. S20. Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) with H2O2 in
different system. (Yellow: YFeO3 system and Red: Ti-YFeO3 system)

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Fig. S21. DMPO-•O2− for different systems after 15-minute visible light irradiation, respectively.

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 Furthermore, it was clear that •OH free radical was the main active species, but how it acts on
pollutants was unclear. In order to study the method of •OH active free radicals working in the
process of pollutant explanation, the degradation products of the model compound 4-chlorophenol
were analyzed by electrospray high resolution mass spectrometry (ESI-HRMS) analysis (Fig. S22
and S23) in negative ion mode (ESI), and the proposed molecular transformation pathways were
inferred (Fig. 4g). Initial substrate 4-chlorophenol (deprotonated excimer ion peak m/z 127 by
ionization in ESI mass spectrometry) was mainly degraded by the substitution, addition, or oxidation
reaction of •OH active species and its degradation pathway mainly showed three reaction channels.
The first reaction channel (down): 4-chlorophenol was oxidized dechlorination atom to form
hydroquinone by •OH active species and then, the ring-opening cracking of benzene ring was
induced by further oxidation to produce small carboxylic acids such as acetic acid, glycolic acid,
buteneic acid and so on. These molecules finally were oxidized and degraded to generate small
molecules of H2O, CO2, H2CO3, etc. The second and third reaction channels (up) were continuous
oxidation of benzene ring followed by oxidative dechlorination. 4-chlorophenol was oxidized to 4-
Chlorobenzene-1,2-diol by substituting the hydrogen on the benzene ring with the •OH active
species. 4-Chlorobenzene-1,2-diol was continue oxidized to form dihydroxy-tetrachlorophenol and
then was oxidized dechlorination (channel 3). 4-Chlorobenzene-1,2-diol was directly oxidized
dechlorination to form phloroglucinol (channel 2). The benzene rings of these molecules were
broken down through the addition reactions, causing them to be degraded into small carboxylic
acids. And they finally were degraded to generate small molecules. In terms of the response
strength of the products (Fig. 4g) obtained from the three different paths, the first and second paths
were more favorable than the third one, which may be due to the highest Fukui index values of the
chlorine groups in 4-chlorophenol’s structure, leading to their preference for •OH species’ attacking3.
As a result, the degradation of p-chlorophenol molecules was more prone to dechlorination followed
by oxidation and deep cracking of the benzene ring.

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 sample-3 #1816 RT: 3.43 AV: 1 SB: 138 0.32-2.48 NL: 1.80E6
T: FTMS - p ESI Full ms [50.0000-600.0000]
sample-3 #1706 RT: 3.23 AV: 1 SB: 156 0.39-2.89 NL: 1.58E6 89
T: FTMS - p ESI Full ms [50.0000-600.0000] 100

90
110
123
100 80

90 70

Relative Abundance
80
60
Relative Abundance

121
70
50
60
40
50

30
40 117
124 87
30 20
116 118
20 122 71 73 85
10
116 87
117 74 85 90
10 120 121 125 72 75 77 79 81 82 83 84 85 86 88 91 92 93 94 95
124 126
117 118 0
116 119 120 121 123 124 126 126
118 119 121 122 123 124 125 125 72 74 76 78 80 82 84 86 88 90 92 94
0
m/z
116 117 118 119 120 121 122 123 124 125 126
m/z

sample-3 #1343 RT: 2.60 AV: 1 SB: 566 0.27-2.39 , 3.98-11.09 NL: 3.45E6 sample-3 #1607 RT: 3.06 AV: 1 SB: 126 0.30-2.27 NL: 6.13E6
T: FTMS - p ESI Full ms [50.0000-600.0000] T: FTMS - p ESI Full ms [50.0000-600.0000]
115
100
110
90
159
100
80
90

80 70
Relative Abundance

Relative Abundance
70 60

60 50

50
40
40
30 115
30
157 20
20
159 161 113
160 114
10 10 116
117 118 125
158 161 162 101 113 119 121 123
156 157 157 158 159 160 161 162 163 102 103 104 105 107 108 109 110 111 112 115 117 120 122 124 125
0 0
156 157 158 159 160 161 162 163 102 104 106 108 110 112 114 116 118 120 122 124
m/z m/z

sample-3 #1545-1870 RT: 2.97-3.51 AV: 29 SB: 149 0.13-2.45 NL: 1.24E5
sample-3 #1717 RT: 3.25 AV: 1 SB: 117 1.11-2.98 NL: 1.08E5 T: FTMS - p ESI Full ms [50.0000-600.0000]
T: FTMS - p ESI Full ms [50.0000-600.0000]
110

109
110 100

59 90
100

90 80

80 70
Relative Abundance
Relative Abundance

70 60

60
50
50
40
40 110
30
30
20
20 108
104 109
10 106 106 107 109 109 110 110
10 105 108
60 104 104
52 54 55 56 58 58 61 61 103 104 105 105 106 106 106 107 107 107 108 109 109 110 110 111
57 0
0 104 105 106 107 108 109 110
51 52 53 54 55 56 57 58 59 60 61 m/z
m/z

sample-3 #1519-1843 RT: 2.91-3.47 AV: 30 SB: 149 0.13-2.45 NL: 1.53E6
T: FTMS - p ESI Full ms [50.0000-600.0000] sample-3 #1596 RT: 3.04 AV: 1 SB: 149 0.13-2.45 NL: 2.96E5
T: FTMS - p ESI Full ms [50.0000-600.0000]

120 110

110 125
100
143
100 90
90
80
80
Relative Abundance

70
Relative Abundance

70
60
60
50
50

40 40

30 30

20 20 123 125
137 138 141 142 123
10 144 145 124
136 136 140 141 147 10 124 125
139 141 143 143 145 146 122
138 138 140 142 145 147 148 123 125
0 124
136 137 138 139 140 141 142 143 144 145 146 147 148 0
m/z 122.0 122.5 123.0 123.5 124.0 124.5 125.0 125.5
m/z

sample-3 #1354 RT: 2.62 AV: 1 SB: 126 0.30-2.27 NL: 3.15E5 sample-3 #1695 RT: 3.21 AV: 1 SB: 117 1.11-2.98 NL: 2.37E5
T: FTMS - p ESI Full ms [50.0000-600.0000] T: FTMS - p ESI Full ms [50.0000-600.0000]
110
110

141 75
100 100

90 90

80 80
Relative Abundance

70 70
Relative Abundance

60 60

50 50

40 40

30 30
140
20 20 74

10 10
142 142 74 77
140 141 76
0 0
139.5 140.0 140.5 141.0 141.5 142.0 142.5 73.5 74.0 74.5 75.0 75.5 76.0 76.5 77.0 77.5
m/z m/z

Fig. S22. Mass spectrum of 4-CP decomposition intermediate products.

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 RT: 0.00 - 20.00
2.91 3.04 NL: 2.53E8
100 2.60 TIC F: FTMS - p ESI Full ms
0.12 3.25 [50.0000-600.0000] MS
0.58 3.66 5.12 6.37 7.58 8.38 9.49
50 9.97 12.10 13.35 14.54 15.45 17.13 18.61 sample-3

0
RT: 3.04 3.31 NL: 5.29E5
100
m/z= 124.50-125.50 F: FTMS
3.47 3.95 - p ESI Full ms
50 2.87 5.58 6.90 7.58 10.34 15.79
1.19 10.92 13.48 17.85 19.74 [50.0000-600.0000] MS
sample-3
0
Relative Abundance

RT: 3.20 NL: 3.43E5

100
m/z= 108.50-109.50 F: FTMS
3.55 - p ESI Full ms
50 2.76 3.94 6.09 [50.0000-600.0000] MS
1.33 6.77 8.71 9.28 11.22 13.08 15.17 16.82 18.19 sample-3
0
2.60 NL: 4.40E6
100
m/z= 158.50-159.50 F: FTMS
- p ESI Full ms
50 RT: 3.14 [50.0000-600.0000] MS
1.60 3.57 3.99 5.58 7.14 8.19 9.45 11.55 12.17 14.30 15.09 17.37 19.27 sample-3
0
RT: 3.14 NL: 9.54E5
100
3.25 m/z= 140.50-141.50 F: FTMS
2.56 - p ESI Full ms
3.55 4.07
50 5.33 6.28 8.05 9.16 [50.0000-600.0000] MS
0.26 2.34 10.79 12.75 14.39 15.91 17.35 18.22
sample-3
0
0 2 4 6 8 10 12 14 16 18 20
Time (min)

Fig. S23. GC-MS information at 30 minutes. The chromatographic images and mass spectrometry
information were shown on the left and right, respectively. At 30 minutes of reaction, C6H5O3−
(m/z=125.02), C6H5O2− (m/z=109.03), C6H4ClO3− (m/z=158.99) and C6H5O4− (m/z=141.02) species
appeared. They belonged to channel 2, 1, 2 and 3, respectively. According to their integral strength,
channel 1 and 2 as the intermediate species may play dominant roles.

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Fig. S24. The structure of YFeO3 and Ti-YFeO3.

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Fig. S25. Calculated H2O2 adsorption energy profiles for Ti sites at Ti-YFeO3 (blue), Fe sites at
pure YFeO3 (yellow) and Fe sites at Ti-YFeO3 (red).

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Table S1. EXAFS fitting parameters at the Fe K-edge for YFeO3 and Ti-YFeO3.

Sample Shell Na R(Å)b σ2(Å2)c R factor

YFeO3 Fe-O 5.10 2.12 0.00464 0.018

YFeO3 Fe-Fe 6.01 3.63 0.00536 0.018

Ti-YFeO3 Fe-O 5.11 2.14 0.00476 0.010

Ti-YFeO3 Fe-Fe 6.05 3.66 0.00787 0.010

aN: coordination numbers; bR: bond distance; cσ2: Debye-Waller factors; R factor: goodness of fit.

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Table S2. Calculated free energy dates for the decomposition Path I and Path II of H2O2 moles
on the surface of YFeO3 and Ti-YFeO3. (The unit is eV.)

Sample H2O2 *H2O2 H-OOH(TS) *OOH+H *OH •OH

YFeO3 0 -4.34192 -3.26166 -4.81457 -3.413 -2.46

Ti-YFeO3 0 -4.43154 -4.03154 -4.69154 -3.20034 -2.46

Sample H2O2 *H2O2 HO-OH(TS) *OH+OH *OH •OH

YFeO3 0 -4.34192 -2.9351 -4.8143 -3.413 -2.46

Ti-YFeO3 0 -4.43154 -3.45461 -4.5143 -3.20034 -2.46

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Table S3. Electrochemical impedance spectrum fitting result in Fig.S4b.

Rs (Ω) Rct (Ω) CPE-T (F) CPE-P (F)

Pure YFO 38.09 9387 7.071E-06 0.968

3% Ti-doped YFeO3 38.74 2969 9.838E-06 0.961

5% Ti-doped YFeO3 38.49 2731 1.003E-06 0.959

7% Ti-doped YFeO3 45.6 4037 6.815E-06 0.971

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SI References

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water splitting. RSC Adv. 7, 18418-18420 (2017).
2. M. Ismael et al., Synthesis of phase pure hexagonal YFeO3 perovskite as efficient visible light
active photocatalyst. Catalysts 7, 326 (2017).
3. F. Li et al., Hydrothermal synthesis of graphene grafted titania/titanate nanosheets for
photocatalytic degradation of 4-chlorophenol: Solar-light-driven photocatalytic activity and
computational chemistry analysis. Chem. Eng. J. 331, 685-694 (2018).

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