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Cooperative Coupling of H2O2 Production and Organic

1. Introduction
Cooperative coupling of photocatalytic H2O2 production with organic
synthesis has an expansive perspective in converting solar energy into Hydroperoxide (H2O2) has received inten-
sive attention as a benign oxidant in
storable chemical energy. However, traditional powder photocatalysts suffer
wastewater treatment, disinfection, and
from severe agglomeration, limited light absorption, poor gas reactant the paper industry.[1,2] Recently, H2O2 is
accessibility, and reusable difficulty, which greatly hinders their large-scale utilized as an energy carrier for the inno-
application. Herein, floatable composite photocatalysts are synthesized by vative one-compartment fuel cell whose
immobilizing hydrophobic TiO2 and Bi2O3 on lightweight polystyrene (PS) theoretical output potential is comparable
to the conventional hydrogen fuel cell.[3]
spheres via hydrothermal and photodeposition methods. The floatable
However, at present, the predominant
photocatalysts are not only solar transparent, but also upgrade the contact method for industrial production of H2O2
between reactants and photocatalysts. Thus, the floatable step-scheme is anthraquinone oxidation, which releases
(S-scheme) TiO2/Bi2O3 photocatalyst exhibits a drastically enhanced H2O2 a large amount of waste and requires high-
yield of 1.15 mm h−1 and decent furfuryl alcohol conversion to furoic acid energy input.[4] Another direct synthesis of
synchronously. Furthermore, the S-scheme mechanism and dynamics H2O2 from H2 and O2 on noble-metal cat-
alysts (e.g., Pd or Au/Pd) suffers from the
are systematically investigated by in situ irradiated X-ray photoelectron
risk of explosion and has not been applied
spectroscopy and femtosecond transient absorption spectrum analyses. In in industrial production yet.[5] Substantial
situ Fourier transform infrared spectroscopy and density functional theory endeavors are devoted to exploring cost-
calculations reveal the mechanism of furoic acid evolution. The ingenious effective methods operated under mild
design of floatable photocatalysts not only furnishes insight into maximizing conditions. Currently, photocatalytic pro-
duction of H2O2 is considered as an alter-
photocatalytic reaction kinetics but also provides a new route for highly
native due to its sustainability.[6–9]
efficient heterogeneous catalysis. Pitifully, photocatalytic H2O2 produc-
tion suffers from rapid charge recombina-
tion and sluggish reaction kinetics. Hence,
hole scavengers are generally employed to solve the dilemma.
However, the use of hole scavengers produces undesirable prod-
B. He, Z. Wang, J. Yu ucts and poses difficulty in mechanism study. In consequence,
State Key Laboratory of Advanced Technology for Materials Synthesis organic synthesis is adopted to resolve this problem.[10,11] Nowa-
and Processing days, organic synthetic chemistry plays an indispensable role in
International School of Material Science and Engineering
Wuhan University of Technology
producing multitudinous fine chemicals.[12] Thereinto, oxida-
Wuhan 430070, P. R. China tion of biomass-derived furanic is significant in refining high-
B. He, Z. Wang, J. Yu, L. Zhang value chemicals and biofuels.[13,14] Specifically, furoic acid (FA),
Laboratory of Solar Fuel which serves as a versatile platform molecule for the synthesis
Faculty of Materials Science and Chemistry of chemicals, can be obtained by photocatalytic oxidation of
China University of Geosciences furfuryl alcohol (FFA).[15] According to the analysis above, it is
Wuhan 430074, P. R. China
E-mail: yujiaguo93@[Link]; zhangliuyang@[Link] intriguing to couple photocatalytic H2O2 production with oxi-
P. Xiao, T. Chen dation of FFA, which eliminates waste of hole scavengers and
Hefei National Laboratory for Physical Sciences at Microscale concurrently realizes energy optimization.
CAS Key Laboratory of Materials for Energy Conversion However, in the conventional photocatalytic system, the
Department of Materials Science and Engineering suspended powder photocatalysts suffer from agglomeration,
University of Science and Technology of China
Hefei 230026, P. R. China
recovery difficulty, limited light utilization, as well as sluggish
delivery of gas-phase reactants.[16,17] These fatal defects retard
The ORCID identification number(s) for the author(s) of this article
can be found under [Link] the enhancement of photocatalytic efficiency in gas-involved
processes and obstruct its industrial application. Fortunately,
DOI: 10.1002/adma.202203225 floatable photocatalysts can solve the aforementioned problems.

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They can float on the solution surface, which increases light demonstrate the successful loading of Bi2O3 (abbreviated as
utilization and enables intimate contact with reactants.[18,19] BO). Moreover, due to the poor crystallinity of photodeposited
Besides, floatable photocatalysts are easy to be separated and Bi2O3, the characteristic peaks in the composite samples are
recycled. Thus, floatable photocatalysts are the optimal choice not so distinct. Therefore, to verify its presence, Raman spectra
for photocatalytic H2O2 production coupled with organic are collected. As shown in Figure S1b, Supporting Information,
synthesis. several characteristic peaks emerge in the Raman spectra of TO
Moreover, in such coupled photocatalytic reactions, photo- and BO. The peaks located at 144, 398, 518, and 640 cm−1 belong
generated electrons and holes are both utilized. Thus, it is a to Eg, B1g, A1g, and Eg vibration modes of the anatase phase.[24]
prerequisite to improve their oxidation and reduction capability. In comparison, the peaks at 125 and 312 cm−1 assigned to A1g
Step-scheme heterojunction, also known as S-scheme hetero- vibration mode in β-Bi2O3 are observed.[25] In the composite
junction, can accomplish the efficient separation of electrons sample, with an increasing ratio of Bi2O3, the peak at 312 cm−1
and holes and meanwhile fulfill maximized oxidation and becomes increasingly visible, indicating its successful loading.
reduction ability.[20,21] The spontaneous migration of electrons Concerning optical properties, the UV–vis diffuse reflec-
leads to the formation of a built-in electric field and facilitates tance spectra of all the samples are acquired. In Figure S1c,
the interfacial charge transfer in the heterojunction.[22,23] The Supporting Information, TiO2 shows an absorption edge at
promoted charge separation and enhanced redox ability of approximately 370 nm in the ultraviolet light region, which cor-
charge carriers assure the two-electron O2-reduction to H2O2 responds to its intrinsic bandgap (Eg) of 3.35 eV. By contrast,
and exhaustive oxidation of FFA. Bi2O3 exhibits slightly narrower absorbance at 384 nm con-
Inspired by the previous discussion, floatable S-scheme verted into a bandgap of 3.23 eV. For the composite catalysts,
TiO2/Bi2O3 photocatalysts based on polystyrene spheres (PSs) a slightly bathochromic shift compared with pristine TO is
are synthesized. And a gas-liquid-solid triphase system is devel- ascribed to the narrower bandgap of BO (in Figure S1d, Sup-
oped by immobilizing hydrophobic TiO2/Bi2O3 on PSs for H2O2 porting Information). Specifically, the absorption intensity
production coupled with FFA oxidation. Thanks to the advan- ranging from 400 to 800 nm barely changes in TBOx, which
tages of floatable photocatalysts, oxygen can rapidly diffuse to implies that the visible light-harvesting capability is preserved.
the solid-water interface and participate in the H2O2 evolution. As characterized by field-emission scanning electron micros-
Simultaneously, the rapid delivery of O2 expedites electron copy (FESEM) in Figure S2a–f, Supporting Information, uni-
consumption and thus minimizes the electron–hole recombi- formly dispersed nanospheres are apparent. In Figure 1b, TiO2
nation. Combining the merits of floatable and S-scheme photo­ precursor is attached to PSs, as evidenced by multiple pits on
catalyst, the H2O2 production rate of TiO2/Bi2O3 can reach the rough surface. After hydrothermal treatment, the homo-
1.15 mm h−1 and the FA formation rate is 0.45 mm h−1. Insights geneous-distributed TiO2 nanocrystals can be observed on the
into the charge transfer and dynamics are obtained from in situ outer surface in Figure 1c. Even after the incorporation of Bi2O3
X-ray photoelectron spectroscopy (XPS) and femtosecond tran- with different proportions, the original spherical morphology is
sient absorption spectroscopy. The reaction path is proposed preserved (Figure S3a–l, Supporting Information). The average
based on DFT calculation and in situ DRIFT results. The recov- diameter of the best-performing TBO40 nanospheres maintains
erable and highly efficient photocatalysts open a promising way at 600 nm (in Figure 1d). As presented in Figure 1e,f, the images
for interface modulation in coupled photocatalytic reactions. obtained on transmission electron microscopy (TEM) at low
and high magnifications indicate that the thickness of TBO40
shell is about 25 nm. Consistent with XRD patterns, the clear
2. Results and Discussion lattice fringe distances of 0.35 and 0.32 nm in the high-reso-
lution TEM (HRTEM) image are indexed to the (101) plane of
2.1. Catalyst Synthesis and Characterization TiO2 and (201) facet of Bi2O3, respectively (Figure 1g). As shown
in corresponding fast Fourier transform (FFT) patterns of the
As elaborated in the schematic diagram (Figure 1a), the TiO2 selected area (Figure 1h), the outer diffraction rings belong to
precursor was obtained by the hydrolysis of titanium isopro- the (321) and (431) planes of tetragonal Bi2O3. Also, the coex-
poxide with the assistance of hexadecylamine (HDA) and isting two inner rings are assigned to the (101) and (103) facets
ammonium hydroxide. Following the hydrothermal process, of anatase TiO2. Furthermore, the high-angle annular dark-field
the highly crystallized TiO2 (abbreviated as TO) nanocrys- (HAADF) image (in Figure 1i) and its corresponding energy-
tals were in situ grown on the surface of the PS sphere. After dispersive X-ray spectroscopy (EDS) (Figure 1j–m) mapping
adding Bi(NO3)3 5H2O with different proportions, the photo­ patterns confirm the uniform distribution of Ti, Bi, and O as
reduction procedure was conducted under illumination in the shell on the PSs. This result suggests the homogeneous dis-
ethylene glycol for the growth of Bi nanoparticles. Ultimately, persion of Bi2O3 nanoparticles due to the uniform adsorption
the TiO2/x%Bi2O3 composite products (denoted as TBOx) were of Bi3+ on TiO2 nanosphere before the photodeposition process.
acquired through oxidation. As shown in Figure 2a–c, the contact angles are measured
As depicted in Figure S1a, Supporting Information, the to examine the hydrophobicity of the TiO2, Bi2O3, and the
crystal structures of as-prepared samples are characterized best-performing TBO40. Owing to the added HDA during the
by X-ray diffraction (XRD). The major peaks in TO and TBOx preparation of the precursor, the alkyl groups still exist in crys-
correspond to the typical anatase TiO2 phase (JCPDS card talline TiO2 after hydrothermal process.[26] Hence, the surface-
No. 21-1272). The labeled emblematic peaks of bismuth oxide alkylated TO shows good hydrophobicity with a water contact
(Bi2O3, JCPDS card No. 27-0050) in the XRD patterns of TBOx angle of 125.9°. By contrast, the contact angle of Bi2O3 is 47.3°,

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Figure 1. a) Synthetic procedures of TBOx via hydrothermal and photodeposition methods. b–d) FESEM images of TiO2-precursor, TO, and TBO40.
e,f) TEM images of TBO40 at low and high magnifications. g) HRTEM image of TBO40, and h) corresponding FFT patterns of the selected area on
TBO40 nanosphere. i) HAADF, and j–m) EDS mapping images of TBO40.

implying its decent hydrophilicity. Therefore, the contact angle or BO. And TBO40 shows the highest production of 1760 µm,
of TBO40 diminishes to 114.3° due to the loading of hydrophilic which is approximately six times higher than TO or BO. The
Bi2O3. As observed in photographs (Figure 2d,e), due to the calculated apparent quantum yield (AQY) of TBO40 can achieve
lightweight PSs and good hydrophobicity, powdery TBO40 is 1.25%. However, when the loading proportion exceeds 40%, the
well-spread on the surface of the liquid, so the redox reactions yield of H2O2 declines, because of the light-shielding effect of
on the floatable photocatalyst are carried out at an air-liquid- self-aggregated Bi2O3.
solid interface (in Figure 2f). Under light illumination, the In the photocatalytic H2O2 production process, the com-
floatable photocatalyst can easily absorb light compared with its petitive formation and decomposition reactions synchronously
suspended counterpart; thus producing more photogenerated influence the activity. Thus, based on the zero-order and first-
electrons and holes. Simultaneously, oxygen rapidly diffuses to order kinetics of H2O2 formation and decomposition, a kinetic
the catalyst–liquid interface. Subsequently, the superoxide rad- equation is shown:[30]
ical evolves and hydroperoxide is generated,[27] FFA is oxidized
into FA by hydroxyl radical (•OH).[28,29] Kf
[ H 2 O2 ] =
Kd
(1 − e −K dt ) (1)
2.2. Photocatalytic Production of H2O2 where Kf (µmol L−1 h−1) and Kd (h−1) are the rate constants of for-
and FA with Stability Tests mation and decomposition, respectively. By fitting the curves in
Figure 3a, the calculated Kf and Kd are presented in Figure 3b.
Photocatalytic tests are conducted in FFA aqueous solution For the single-component catalyst, as expected, TO and BO
under the 300 W Xe lamp. As depicted in Figure 3a, both pris- show low formation rates and high decomposition rates. And
tine TO and BO show low H2O2 production of ≈300 µm in the Kf gradually increases to 1772.6 µm h−1 when the loading
1 h, which is attributed to the rapid recombination of photo- proportion reaches 40% and then it decreases. Different from
generated electron–hole pairs. When the heterojunctions are the variation tendency of Kf, the decomposition rates of TBO10
constructed in TBOx, the photocatalytic performance of com- and TBO20 rise slightly compared with TO and BO at first.
posite catalysts is greatly enhanced. With increasing Bi2O3, the While as the amount of Bi2O3 increases, the Kd declines. In the
activity rises gradually at first, reaching two to fourfolds of TO extra degradation experiments in N2, TBO40 has the minimum

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Figure 2. a–c) The contact angle photographs on tablets of TO (a), BO (b), and TBO40 (c). d,e) Photographs of the floatable catalyst. f) Schematic
illustration of photoredox reaction in the triphase system.

H2O2 decomposition rate (in Figure 3c), in agreement with the (HPLC) was adopted to investigate the FFA oxidation to FA.
previous fitting results. This phenomenon suggests that the As presented in the 12 h-stability test, the production of H2O2
optimal deposition of Bi2O3 can efficiently inhibit H2O2 decom- and FA steadily increase (in Figure S4a,b, Supporting Infor-
position by electron reduction (H2O2 + H+ + e− → H2O + •OH), mation). As expected, in Figure 3d, TBO40 shows the highest
which is also ascribed to the constant consumption of photo- FA production rate at 0.45 mm h−1, corresponding to its H2O2
generated electrons by sufficient O2 in a tri-phase system. production rate at 1.15 mm h−1, which is much higher than
For organic synthesis, FFA oxidation occurs at the interface of TO (0.093 mm h−1) and BO (0.067 mm h−1). And, as shown in
catalyst/liquid. And, high-performance liquid chromatography Table S1, Supporting Information, TBO40 outperforms various

Figure 3. a) Photocatalytic production of H2O2 under irradiation by a 300 W Xe lamp (spectral region: ≈350–780 nm) for an hour and b) the fitting
formation rate constant (Kf) and decomposition rate constant (Kd) of TO, BO, and TBOx. c) Time-dependent H2O2 decomposition curves of the pre-
pared samples under Xe lamp irradiation (initial concentration of H2O2: 1 mm). d) Production formation rates of H2O2 (red) and FA (blue) over TO,
BO, and TBO40 in 12 h.

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photocatalysts in H2O2 generation coupled with organic syn- versus Ag/AgCl under irradiation. Among all the samples,
thesis. Additionally, the production rates of TBO40 in the tradi- TBO40 shows the smallest semicircle radius (Figure S5d, Sup-
tional biphase system are tested for comparison. In Figure S4c,d, porting Information), revealing its lowest charge transfer resist-
Supporting Information, despite TBO40 exhibiting steady ance contributed by excellent bulk-to-surface charge transfer
12 h-production of H2O2 and FA in the biphase system, the evo- ability.[38]
lution rates reduce by 25% compared to the triphase system.
Furthermore, the obtained product in the triphase system is
also detected by gas chromatography-mass spectrometry (GC- 2.4. Band Structures and Photocatalytic Mechanism
MS) and corresponding spectra are presented in Figure S4e,f,
Supporting Information. The mass spectrum is in good con- To further investigate the band structures of TO and BO, Mott–
sistency with the FA standard, and agrees with the previous Schottky (M–S) and ultraviolet photoelectron spectroscopy
HPLC test. (UPS) curves are acquired. In Figure S6, Supporting Informa-
tion, the slopes of TO and BO are both positive, which are asso-
ciated with their n-type properties, and the flat band potentials
2.3. Charge Transfer and Separation Characterizations are extrapolated to −0.1 and −0.4 V, respectively. Combining
UPS analysis (in Figure S7, Supporting Information) and lit-
Steady-state photoluminescence (PL) and time-resolved photo- erature,[39] the staggered band structures of TO and BO are
luminescence (TRPL) spectra are acquired to reveal the elec- depicted in Figure S8a, Supporting Information. The conduc-
tron–hole recombination and migration dynamics. As shown tion band (CB) bottom potentials of TO and BO are approxi-
in Figure S5a, Supporting Information, the primary emission mately −0.4 and −0.9 V (vs normal hydrogen electrode (NHE),
peaks situated at ≈380 and ≈390 nm for TO, BO and TBOx are pH = 0) and the valence band (VB) top potentials are 2.9 and
attributed to the recombination of photoexcited charge carriers 2.3 V referring to the bandgap energies from the UV–vis
through band-to-band transitions.[31] For TO and its composites, spectra, respectively. The contact potential differences (CPDs)
the PL peaks situated at 450 and 468 nm are due to band edge are measured quantitatively by Kelvin probe to calculate the
free exciton annihilation of anatase TiO2, whereas the rest cen- work function (WF) (in Figure S8b, Supporting Information).
tered at 482 and 493 nm are attributed to the bound excitons. The measured CPD values of TO, BO, and TBO40 in the dark
Furthermore, the emission intensity of TBO40 is much lower are 397.8, −203.9, and 298.1 mV (in Table S3, Supporting Infor-
than that of TO, indicating the suppressed charge recombina- mation). Thereby, their corresponding Fermi levels are 0.15,
tion.[32,33] In Figure S5b, Supporting Information, TRPL spectra −0.45, and 0.05 V, respectively. These results are consistent
are obtained to investigate the fluorescence lifetime and relaxa- with the previous deduced band structure. When illuminated
tion process of photogenerated charges. The decay curves of by 369 nm light, the CPD values of all the samples decrease,
TO, BO, and TBO40 can be fitted by the tri-exponential equa- re-confirming their n-type characteristic.
tion in which τ1, τ2, and τ3 refer to the lifetimes (ns) for the As shown in Figure S8c,d, Supporting Information, the
radiative, non-radiative, and energy transfer processes, respec- superoxide anion radicals (·O2−) and hydroxyl radicals (·OH)
tively.[34] The average lifetime (τa) is calculated according to the are monitored by electron paramagnetic resonance (EPR)
following equation: during photocatalytic reactions. For single-component cata-
lysts, both TO and BO show DMPO-·O2− signals in metha-

τa =
(A τ 1
1 2 + A2τ 22 + A3τ 23 )
(2)
nolic suspension after illumination for 5 min, indicating their
( A1τ 1 + A2τ 2 + A3τ 3 ) reduction potentials are more negative than O2/·O2− at −0.33 V.
However, the DMPO-·OH signals can only be observed for TO
As summarized in Table S2, Supporting Information, in in aqueous solution, which means that BO is incapable to oxi-
TBO40, a relatively small τ1 (0.49 ns) is witnessed and it contrib- dize OH− into ·OH (at 2.37 V vs NHE, pH = 0). Nevertheless,
utes the most (62.78%). At the same time, the shorter τ2 and τ3 when the heterojunction is constructed, the stronger signals of
of TBO40 imply the elevated non-radiative attenuated efficiency. DMPO-·O2− and DMPO-·OH can be simultaneously observed.
The reduced average lifetime (τa) of TBO40 compared with TO This phenomenon demonstrates that the charge transfer
and BO signifies the promoted electron–hole separation and between TO and BO does not abide by the conventional type-II
accelerated charge transfer at the interface of heterojunction.[35] mechanism. Instead, it follows the S-scheme mechanism.[40]
Transient photocurrent curves obtained under chopped To validate the above conjecture of S-scheme mechanism, in
light illumination for several cycles are shown in Figure S5c, situ irradiated XPS is adopted to investigate the directions of
Supporting Information. The photocurrent density of TBO40 electron transfer. The peaks centered at 458.3 and 464.2 eV in Ti
remains stable and reaches −0.8 µA cm−2, which increases 2p XPS spectrum of pristine TiO2 (Figure 4a) are ascribed to Ti
twofold and fourfold of BO and TO, respectively. This result 2p3/2 and Ti 2p1/2, respectively. After the deposition of Bi2O3 on
verifies the rapid charge transfer and facilitated electron–hole the TiO2 surface, the peaks of Ti 2p3/2 and Ti 2p1/2 shift nega-
separation in the composite.[36] As observed in TiO2-based sam- tively by ≈ 0.2 eV, indicating increased electron density in TiO2.
ples, the current decreases immediately after the light switches When TBO40 is irradiated, the peaks move in the opposite
off and then declines gradually. This is caused by the release of direction, which means the electrons transfer from TO to BO.
charge carriers from deep traps.[37] Furthermore, to investigate As for Bi (Figure 4b), the 3d5/2 and 3d3/2 peaks of BO situate
photoelectron transfer capability, the electrochemical imped- at 159.3 and 164.6 eV. Contrary to Ti, the peaks of Bi in TBO40
ance spectra (EIS) of TO, BO, and TBO40 are recorded at −1.0 V migrate to higher binding energy by ≈ 0.3 eV compared to that

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Figure 4. a,b) High-resolution XPS spectra of: a)Ti 2p in TO, TBO40, and TBO40 under 365 nm LED irradiation; b) Bi 4f in BO, TBO40, and TBO40-
UV; and c) O 1s spectra of TO, BO, TBO40, and TBO40-UV. d) WF (or Fermi levels) of TiO2 and Bi2O3 before and after the contact and electron-transfer
mechanism of the S-scheme heterojunction under light irradiation.

of BO at first, and then slightly decrease under illumination. tron transfer mechanism and dynamics. Instantly after
This phenomenon suggests the electrons transfer from BO to excitation, the fs-TA spectrum of TO shows a prominent
TO when the heterojunction is formed and the photogenerated peak at 395 nm with negative ΔOD at different time delays
electrons backflow to BO from TO under irradiation.[41] Besides, (in Figure 5a), which is assigned to ground state bleach
the O 1s spectrum of TO shown in Figure 4c can be deconvo- (GSB).[48–50] In addition, a much weaker and broader excited-
luted into peaks located at 529.5, 531.1, and 532.9 eV, which are state absorption (ESA) band can be observed from 425 to
accredited to the lattice oxygen, hydroxyl groups, and absorbed 550 nm (in Figure S9a, Supporting Information). The TA
H2O, respectively. Because of the larger electronegativity of spectra of TO with AgNO3 (electron scavenger) and FFA
Bi, the peak of lattice O2− in BO and TBO40 centers at higher (hole scavenger) are also obtained. As shown in Figure S9b,
binding energy compared with TO.[42] Supporting Information, after adding AgNO3, the GSB peak
Figure 4d shows the electron transfer mechanism of the decreases; while the broad peak around 450 nm becomes
S-scheme between TiO2 and Bi2O3. Bi2O3 is an n-type semicon- more obvious. Besides, the GSB peak becomes weaker in the
ductor photocatalyst with a smaller WF of 4.05 eV and a higher presence of the FFA and the broad peak centered at 500 nm
Fermi level (−0.45 V vs NHE, pH = 0). Relatively speaking, intensifies (in Figure S9c, Supporting Information). Hence,
TiO2 shows a larger WF of 4.65 and a lower Fermi level (0.15 V photo­ excited electrons and holes in TO contribute to both
vs NHE, pH = 0). So, when TiO2 and Bi2O3 come into contact, GSB and broad ESA signals.[51,52] Additionally, all the kinetics
electrons in Bi2O3 spontaneously migrate to TiO2. Subsequently, are analyzed by fitting with convoluted multi-exponential. By
the Fermi levels bend gradually in the interface region and only fitting the curves of TO-FFA (Figure S9d, Supporting Infor-
equalize at the exact contacting point without changing the mation), the average electron lifetime (τave) is calculated to
Fermi levels of TO or BO.[43,44] Thus, the charge redistribution be 2.8 ps, which is smaller than the fitted τave (3.2 ps) of TO
leads to the band bending and the formation of an internal elec- without a hole scavenger. This is because holes contribute par-
tric field at the interface of the heterojunction. Afterward, under tially to the charge decay process of TO. When TBO40 het-
solar illumination, electrons in TiO2 and Bi2O3 are individually erojunction is constructed, the attenuated peak at 395 nm
excited from VB to CB. With the synergistic effect of an internal and more distinct peak at 450 nm (in Figure 5b) are similar
electric field, band bending and Coulombic attraction, the photo- to those in TO-AgNO3, implying the electron-exacting feature
generated electrons on CB of TiO2 are inclined to transfer to the of Bi2O3. In other words, electrons flow from the CB of TO to
VB of Bi2O3.[21,45] Meanwhile, the photoinduced charge carriers BO (in Figure 5d), which again authenticates S-scheme charge
with supreme redox capacity are preserved to engage in photo- transfer. In addition, the decay rate of holes in TBO40 during
catalytic H2O2 production and FFA oxidation reactions.[46,47] the first 100 ps prolongs to 232.5 ps compared with that of TO
Furthermore, femtosecond transient absorption (fs-TA) (148.5 ps), indicating the suppressed photogenerated charge
spectrum is obtained to gain a deep insight into the elec- recombination in TBO40 (Figure 5c).[53]

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Figure 5. a,b) The transient absorption spectrum of TO (a) and TBO40 (b) recorded with 340 nm excitation. c) Corresponding fitted transient
absorption kinetics of TO-AgNO3 and TBO40 at 395 nm within 100 ps. d) Schematic illustration of S-scheme charge transfer within the TBO40
heterojunction.

To detect the reaction intermediates in the FFA oxidation As analyzed by DRIFTS results above, the speculated photo­
process, in situ diffuse reflectance infrared Fourier transform catalytic reaction step is summarized in Figure 6d. Firstly,
spectroscopy (DRIFTS) measurements are conducted in dark- under solar irradiation, the photoexcited electrons transfer
ness for organic adsorption for the first 1 h and under irradia- from lattice oxygen to the adjacent Ti4+, parallelly creating a
tion for another 1 h. Initially, FFA molecules are adsorbed on charge-separated state. With the adsorption of FFA molecules,
the Lewis acidic sites in TiO2 under the dark condition when the α-hydrogen of FFA is removed and the deprotonated alco-
FFA gas is introduced.[54] In Figure 6a, a new infrared peak holate group is chemically adsorbed on Ti4+. Following the
at 732 cm−1 for the β-ring bending vibration of furan ring in electron transfer from lattice oxygen to the adjacent Ti4+ and
furan derivatives is detected. As shown in the enlarged view in hole transfer to C5, the β-hydrogen in the alcoholate group is
Figure 6b,c, peaks ranging from 1470 to 1560 cm−1 are the ring removed, producing the carbon radical.[57,58] In addition, the
breathing mode. In addition, the absorption bands at 1146, elevated carbon-centered radicals are detected by EPR spec-
1507, and 1588 cm−1 are assigned to C1OC4, C1C2, and trometer (in Figure S10, Supporting Information). Subse-
C3C4 of the furan ring, respectively (the order of C is marked quently, the photogenerated hole reacts with OH− to produce
out in Figure 6d).[55] Another absorption peak at 2925 cm−1 is ·OH. Then, the carbon radical is desorbed from Ti3+ sites and
ascribed to the asymmetric stretching vibration of methylene reacts with the hydroxyl radical. After further dehydrogenation,
(C5H2). And, the peak at 1105 cm−1 indicates that FFA is lin- the complex finally transforms into FA.
early adsorbed on Ti4+ by O-terminal C5O bond.[56] As the Based on the proposed reaction mechanism, density functional
oxidation reaction proceeds, the peak centered at 1717 cm−1 theory (DFT) calculations are conducted on a (101) slab of TiO2 to
assigned to the physically adsorbed furfural (FF) is observed further validate the preference for FA generation. As shown in the
as the crucial intermediate. Besides, vertical adsorption by free energy diagram (Figure 6e and Table S4, Supporting Informa-
C5O of FF through the O terminal is demonstrated by the tion), the rate-determining step is the first deprotonation process
peak at 1699 cm−1.[56] Gradually, the stretching vibration peak of α-hydrogen on oxhydryl (*RCH2OH − H+ + h+ → *RCH2O)
of furoic acid emerges at 1167 cm−1 and the peak at 2855 cm−1 with the energy barrier of 2.94 eV. For the generation of R-CHO,
becomes weaker, indicating further oxidation from FF to FA. the ΔG of RCHO is calculated to be 1.94 eV. By contrast, the con-
Furthermore, the characteristic band of C5O stretching in version of *RCHO into *RC(OH)2 is thermodynamically spon-
FA situated at 1684 cm−1 gradually enhances with the lapse taneous with ΔG of −0.48 eV. Therefore, the adsorbed *RCHO
of time. intermediate prefers being further oxidized to desorbed.

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Figure 6. a) The in situ DRIFT spectra of TBO40 in darkness in the first 60 min and under illumination for another 60 min with the test interval of
10 min. b) The enlarged view of the yellow marked area from 1000 to 1500 cm−1 in DRIFT spectra. c) Detailed image of the blue marked area from 1500
to 1750 cm−1 in DRIFT spectra. d) The proposed mechanism of photocatalytic FFA oxidation coupling with H2O2 production with the existence of O2
on TBO40 surface. e) Free energy diagrams of FFA oxidation steps on active sites (*) of TiO2.

Simultaneously, as observed in the former EPR tests, the (Figure S11a, Supporting Information), the numbers of trans-
distinct peaks of ·O2− indicate the continuous single-electron ferred charges are calculated to be 1.0, 1.1, and 1.3 for TO,
reduction to H2O2 as follows: BO, and TBO40, respectively, implying that H2O2 production
is a multi-step consecutive single-electron reduction process.
O2 + e − → ·O2− (3) Meanwhile, the trapping experiments using 1,4-benzoquinone
(•O2− scavenger), isopropanol (•OH scavenger), and trietha-
·O2− + e − + 2H+ → H2O2 (4) nolamine (h+ scavenger) were carried out to explore the pri-
mary reactive intermediate for H2O2 production. As shown in
To verify the proposed pathway, the number of transferred Figure S11b, Supporting Information, over 90% reduc-
charges is obtained by fitting the polarization current curves of tion in H2O2 yield can be observed after the addition of
TO, BO, and TBO40. As shown in the Koutecky–Levich plots ­1,4-benzoquinone, which is consistent with the EPR results.

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Figure 7. a,b) Schematic illustrations of the O2 flow supply for the photocatalyst in biphase (a) and triphase (b) systems for O2 reduction and FFA
oxidation.

Contrarily, in the •OH trapping experiments, the H2O2 yield over floatable photocatalyst in a multi-phase system and is also
slightly decreases, which is probably ascribed to the promoted referential for other photocatalytic applications.
H2O2 decomposition process (H2O2 + H+ + e− → H2O + •OH).
In addition, when the h+ is arrested by triethanolamine, the
decay is inconspicuous as expected. The results also reinforce Supporting Information
the O2 reduction pathway above. Supporting Information is available from the Wiley Online Library or
Of note, traditional solid photocatalyst has to be firstly dis- from the author.
persed in the liquid phase and bubbled with oxygen to reach
saturation. And the subsequent reaction is greatly hindered by
the insufficient dissolved O2 (8.38 mg L−1 at 25 °C) (Figure 7a) Acknowledgements
and intrinsic electron–hole recombination due to the sluggish
This work was supported by the National Natural Science Foundation
kinetics. Distinctively, in Figure 7b, as for the floatable photo­ of China (NSFC) (Nos. 52073223, 51872220, 51932007, 51961135303,
catalyst, the redox reactions occur at the separate gas-liquid-solid 21871217, and U1905215).
tri-phase interface. The continuous supply of gas reactants tre-
mendously speeds up the dynamics and thus reduces the possi-
bility of electron–hole recombination. Sufficient O2 is reduced to Conflict of Interest
•O − with enhanced H O production. Simultaneously, the active
2 2 2
The authors declare no conflict of interest.
sites on floatable photocatalyst are more accessible to FFA. Not
only that, as proved by the photocatalytic performance above, the
production of FA is stable and H2O2 decomposition is greatly Author Contributions
improved by the floatable photocatalyst.
B.H. and J.Y. conceived the research. B.H. synthesized the catalysts, and
performed the structure analysis and photocatalytic tests. Z.W. carried
out the DFT calculations. B.H., P.X., and H.C. performed the ultrafast
3. Conclusion TA measurements. B.H. wrote the manuscript. J.Y. and L.Z. supervised
the research. All authors discussed the results and commented during
A floatable photocatalyst is designed for H2O2 production cou- manuscript preparation.
pled with FFA oxidation at the air–liquid–solid interface. It is
synthesized by immobilizing hydrophobic TiO2/Bi2O3 on PS
spheres, enabling the sustained and adequate supply of O2 and Data Availability Statement
FFA molecules. Meanwhile, the analysis of in situ XPS and
The data that support the findings of this study are available from the
fs-TA indicates that the charge transfer in the composite com- corresponding author upon reasonable request.
plies with S-scheme heterojunction, which significantly reduces
electron–hole recombination and simultaneously possesses the
maximized reduction and oxidation ability. Because of their syn- Keywords
ergistic effect, the optimal sample exhibits a superb photocata-
photocatalytic furfuryl alcohol oxidation, photocatalytic hydrogen
lytic H2O2 generation rate at 1.15 mm h−1 and an FA production
peroxide production, step-scheme photocatalysts, triphase systems
rate of 0.45 mm h−1. Furthermore, in situ DRIFT test and DFT
calculations provide direct evidence for the oxidation pathway Received: April 10, 2022
on Lewis acidic sites of TiO2 from FFA to FA. This work paves Revised: July 15, 2022
a new way for H2O2 production coupled with organic oxidation Published online: August 22, 2022

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