Solid Base Bi24O31Br10(OH)δ with Active Lattice Oxygen for the Efficient Photo-Oxidation of Primary Alcohols to Aldehydes

Article abstract of DOI:10.1002/anie.201900773

The selective oxidation of primary alcohols to aldehydes by O₂ instead of stoichiometric oxidants (for example, Mn^VII, Cr^VI, and Os^IV) is an important but challenging process. Most heterogeneous catalytic systems (thermal and photocatalysis) require noble metals or harsh reaction conditions. Here we show that the Bi₂₄O₃₁Br₁₀(OH)_δ photocatalyst is very efficient in the selective oxidation of a series of aliphatic (carbon chain from C₁ to C₁₀) and aromatic alcohols to their corresponding aldehydes/ketones under visible-light irradiation in air at room temperature, which would be challenging for conventional thermal and light-driven processes. High quantum efficiencies (71 % and 55 % under 410 and 450 nm irradiation) are reached in a representative reaction, the oxidation of isopropanol. We propose that the outstanding performance of the Bi₂₄O₃₁Br₁₀(OH)_δ photocatalyst is associated with basic surface sites and active lattice oxygen that boost the dehydrogenation step in the photo-oxidation of alcohols.

Full text of DOI:10.1002/anie.201900773

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Accepted Article
Title: Solid Base Bi24O31Br10(OH)δ with Active Lattice Oxygen for
Efficient Photo-oxidation of Primary Alcohols to Aldehydes
Authors: Yitao Dai, Pengju Ren, Yaru Li, Dongdong Lv, Yanbin
Shen, Yongwang Li, Hans Niemantsverdriet, Flemming
Besenbacher, Hongwei Xiang, Weichang Hao, Nina Lock,
Xiaodong Wen, James P. Lewis, and Ren Su
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201900773
Angew. Chem. 10.1002/ange.201900773
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10.1002/anie.201900773
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Solid Base Bi24O31Br10(OH)δ with Active Lattice Oxygen for
Efficient Photo-oxidation of Primary Alcohols to Aldehydes
Yitao Dai, Pengju Ren, Yaru Li, Dongdong Lv, Yanbin Shen, Yongwang Li, Hans Niemantsverdriet,
Flemming Besenbacher, Hongwei Xiang, Weichang Hao, Nina Lock, Xiaodong Wen, James P. Lewis
and Ren Su*
3c]
Abstract: Selective oxidation of primary alcohols to aldehydes by O2
instead of stoichiometric oxidants (e.g., Mn7+, Cr6+ and Os4+) is an
important but challenging process. Most heterogeneous catalytic
systems (thermal- and photo-catalysis) require noble metals or harsh
reaction conditions. Here we show that the Bi24O31Br10(OH)δ
photocatalyst is very efficient in selective oxidation of a series of
aliphatic (carbon chain from C1 to C10) and aromatic alcohols to their
corresponding aldehydes/ketones under visible light irradiation in air
at room temperature, which would be challenging for conventional
thermal- and light-driven processes. Representatively, high quantum
efficiencies (71% and 55% under 410 and 450 nm irradiation) are
reached for the oxidation of isopropanol. We propose that the
outstanding performance of the Bi24O31Br10(OH)δ photocatalyst is
associated with surface basic sites and active lattice oxygen that
boost the dehydrogenation step in the photo-oxidation of alcohols.
for the selective oxidation of primary alcohols.[3a,
Although
these thermal catalytic systems can realize selective conversion
of primary alcohols to aldehydes, the use of noble metals or
harsh reaction conditions are obvious drawbacks.
Photocatalytic alcohol oxidation is a promising process, as it
can be performed using solar energy under mild conditions (e.g.,
room temperature and ambient pressure).[4] Supported noble
metal nanoparticles (NPs) (i.e., Pt[4b] and Au[4d]) are effective
photocatalysts for the oxidation of primary alcohols. Although the
reaction can be realized under mild conditions using O2 as
oxidant, these systems still need to employ noble metals.
Moreover, it is also worth noting that most reported
photocatalysts are only effective in the oxidation of aromatic
alcohols (e.g., benzyl alcohol),[4e, 4f, 5] which are more active than
that of aliphatic alcohols. Upon the non-noble metal
photocatalyst systems, bismuth based photocatalyst materials
are considered as promising candidates (i.e., BiOBr[5j], BiOCl[4f]
,
Bi12O17Cl[5h] and Bi2WO6[5k]), which show excellent performances
in photocatalytic oxidation of organic pollutants.[6] Up to date,
efficient selective oxidation of primary aliphatic alcohols is still a
challenge for aforementioned photocatalysts. For example, the
supported noble metal photocatalyst only presents reasonable
performance in 1-hexanol oxidation (49% Con. And 63% Sel.)
and is inactivity for C7-C10 alcohol conversion.[4d]
Selective oxidation of primary alcohols to aldehydes is of high
significance, as aldehydes are valuable intermediates in organic
synthesis and important compounds for the perfume industry.[1]
However, the synthesis of aldehydes in most cases has to use
strong oxidizing agents that are expensive, toxic or harmful to
the environment (i.e., CrO4 , MnO4 , and Os4+).[2] Several
heterogeneous thermal catalytic systems have been developed
for the oxidation of primary alcohols.[1b, 1c, 3] For example, a Pd(II)
complex has been applied for pentan-1-ol oxidation, and a good
2-
−
o
yield in a biphasic water-alcohol system is achieved at 100 C
and 3 MPa air under basic conditions.[1b] It has also been
reported that noble metal (i.e., Au, Au-Pd) nanoparticles (NPs)
loaded on oxide supports (i.e., CeO2, TiO2) are active catalysts
[*]
Dr. Y. Dai, Dr. P. Ren, Y. Li, Dr. Y. Shen, Prof. Dr. Y. Li, Prof. Dr. H.
Xiang, Prof. Dr. J.W. Niemantsverdriet, Prof. Dr. X. Wen, Dr. R. Su
SynCat@Beijing, Synfuels China Technology Co. Ltd.
Leyuan South Street II, No.1, Yanqi Economic Development Zone
C#, Huairou District, Beijing, 101407 (China)
E-mail: suren@synfuelschina.com.cn
Dr. Y. Dai and Dr. P. Ren contributed equally to this work.
Dr. Y. Dai, Prof. Dr. F. Besenbacher, Dr. N. Lock
Interdisciplinary Nanoscience Centre (iNANO)
Aarhus University
Scheme 1. Illustration of the Bi24O31Br10(OH)δ photocatalyst with surface
basic sites and active lattice oxygen (yellow) for oxidation of alcohol to
aldehyde in air under visible light irradiation. The extracted hydrogen atoms
from alcohol hydrogenates the photocatalyst (black), which eventually react
with active lattice oxygen and molecular O2 to form water (white atoms: H,
grey atoms: C, and red atoms: O).
Gustav Wieds Vej 14, DK-8000 Aarhus C (Denmark)
D. Lv, & Prof. Dr. W. Hao
Center of Materials Physics & Chemistry, Department of Physics,
Beihang University, Beijing 100191, P. R. China
Prof. Dr. J.W. Niemantsverdriet
SynCat@DIFFER, Syngaschem BV
6336 HH Eindhoven (The Netherlands)
Apparently, an efficient and cheap (noble-metal free) catalyst
with a broad scope of substrates is needed for the selective
oxidation of primary alcohols to aldehydes, and of secondary
alcohols to ketones, under mild reaction conditions. Previous
studies show that the acid-base properties of metal oxide
catalysts (e.g., MgO, MoO3 and WO3) determine the alcohol
dehydration and/or dehydrogenation processes.[7] While
isopropanol is oxidized to acetone via dehydrogenation over
Prof. Dr. Y. Li, Prof. Dr. H. Xiang, Prof. Dr. X. Wen and Prof. Dr. J.
P. Lewis
State Key Laboratory of Coal Conversion, Institute of Coal
Chemistry, CAS, Taiyuan, 030001, (China)
Prof. Dr. J. P. Lewis
Department of Physics and Astronomy, West Virginia University,
Morgantown, WV 26506-6315 (USA).
Supporting information for this article is given via a link at the end of
the document
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10.1002/anie.201900773
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basic catalysts, propene is formed via dehydration over acid
catalysts.[7e, 8] Therefore, we anticipate that the combination of
base catalysis and photocatalysis may promote the photo-
oxidation of primary alcohols.
Here we show that the solid base Bi24O31Br10(OH)δ
photocatalyst with active lattice oxygen is efficient in selective
photo-oxidation of various alcohols in air under visible light
irradiation. A series of primary alcohols with different carbon
chain length (C1 to C10), a secondary alcohol (isopropanol) and a
number of aromatic alcohols with different substituents all
the Supporting Information). The O1s spectrum of
Bi24O31Br10(OH)δ consists of three peaks, one corresponds to the
lattice oxygen (OL, 529.8 eV) and the other two are hydroxyl
groups (531.2 eV) and surface adsorbed water (532.8 eV).[9a, 9c]
This assignment is supported by the XPS spectrum of a
commercial Bi(OH)3 reference that exhibits
a similar O1s
spectrum with an additional peak at 532.1 eV due to water
adsorption.[10] Furthermore, the survey spectrum shows that the
sample solely contains the elements Bi, O and Br, with a Bi/Br
ratio of 3.9 (Supporting Information, Figure S1a), suggesting a
convert to their corresponding aldehydes or ketone. For instance, Br-deficient surface (in comparison with a Bi/Br ratio of 2.4 for
high apparent quantum efficiencies (QE) are obtained for the
isopropanol oxidation (71% at 410 nm and 55% at 450 nm
irradiation). The remarkable performance in alcohol oxidation is
ascribed to the accelerated photocatalytic hydrogen extraction
step, which results from a synergetic effect of surface basic sites
and active lattice oxygen (Scheme 1).
the stoichiometric bulk material).
According to transmission electron microscopic imaging
(TEM, Figure 1c), the as-synthesized Bi24O31Br10(OH)δ has a
porous nanostructure that consists of flower-like networks with
sizes up to ~2 µm. The open structure results in a surface area
of 45 m2·g-1 according to nitrogen adsorption isotherm. The
loose and porous architecture allows easy diffusion of bulky
alcohols to access the abundant surface active sites.
Bi24O31Br10(OH)δ presents a visible light response extending into
the green light region (bandgap of ~2.5 eV, Figure S2 in the
Supporting Information). According to Mott-Schottky analysis
reported previously,[9d, 11] the conduction band minimum (CBM)
and valence band maximum (VBM) of the Bi24O31Br10 are
located at ~-0.5 – -0.8 V and ~ 1.7 – 1.9 V vs. the standard
hydrogen electrode (SHE), suggesting that alcohol oxidation and
O2 reduction are thermodynamically feasible (Figure 1d).
Table 1. Photocatalytic oxidation of a series of alcohols (primary alcohols C1-
C10, cyclohexanol C6 and substituted benzyl alcohols) using Bi24O31Br10(OH)δ
in 1 bar air at RT under visible light irradiation.[a]
Alcohol substrates
CH3OH
Carbonyl Products
CH2O
Con. /%
84
81
Sel. /%
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
79
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
95
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
Figure 1. a) XRD pattern of the as-synthesized Bi24O31Br10(OH)δ. b) High
resolution XPS spectra of O1s for Bi24O31Br10(OH)δ with commercial Bi(OH)3
as reference. c) TEM (100 nm scale bar) and d) band positions of the
Bi24O31Br10(OH)δ sample. The redox potentials of O2 and isopropanol are also
shown as references.
97
≥ 99
≥ 99
≥ 99
≥ 99
≥ 99
O
F
O
Cl
O
The Bi24O31Br10(OH)δ photocatalyst is synthesized via a
facile microwave-assisted method in an alkaline aqueous
solution (pH ≈ 13, see Supporting Information). The powder X-
ray diffraction (PXRD) pattern (Figure 1a) reveals that all
diffraction peaks correspond to monoclinic Bi24O31Br10 (JCPDS
card No. 75-0888). The (002) peak of our sample is shifted to a
lower angle (~ 9o) compared to the value (10.6o) reported in
literature,[9] indicating an increased interplanar distance of the
layered material, which may be ascribed to the partial
replacement of Br- by OH- due to the strong basic environment.
This intercalating effect of OH- is confirmed by X-ray
photoelectron spectroscopy (XPS, Figure 1b and Figure S1 in
H3C
OH
H3CO
[a] Reaction conditions:
8 mM reactant and 50 mg catalyst in 10 mL
acetonitrile in air at RT under 450 nm LED (0.03 W·cm-2) irradiation for 24
hours for aliphatic alcohols and 4 hours for aromatic compounds.
Table 1 summarizes the performances of Bi24O31Br10(OH)δ in
photo-oxidation of various alcohols in air at room temperature
(RT, Supporting Information, Figure S3). Blank tests show that
no reaction takes place without irradiation or without
photocatalyst. The primary alcohols with carbon chain lengths
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from C4 to C10 fully convert to their corresponding aldehydes with
high selectivity (≥ 99%) during 24 hours of blue light irradiation
(450 nm). The alcohols with short chain length (methanol,
achieved under 410 nm and 450 nm irradiation, respectively.
Note also that a reasonable QE of 3% is even obtained under
green light irradiation (530 nm). Hence, the QE action spectrum
roughly matches the light absorption curve of the
Bi24O31Br10(OH)δ photocatalyst, suggesting an efficient utilization
of light. In addition, the Bi24O31Br10(OH)δ photocatalyst exhibits a
stable performance in photocatalytic conversion of benzyl
alcohol into benzaldehyde within five consecutive runs (Fig. 2d),
suggesting its promising potential in applications.
ethanol and propanol) present
(conversion of ~80%), which may be due to a relatively weaker
polarizability[12] and
different reaction path between the
a slightly lower reactivity
a
photogenerated holes and the alcohol substrates.[13] Moreover,
the methanol photo-conversion increases with increasing
irradiation time, suggesting pseudo-first-order kinetics of the
alcohol oxidation (Supporting Information, Figure S4). We
expect that this reaction would also reach 100% conversion by
extending the reaction time.
The aromatic alcohols oxidize considerably faster than their
aliphatic counterparts. Benzyl alcohols with different functional
groups (e.g., p-NO2, p-F, p-Cl, p-CH3 and p-OCH3) fully convert
to their corresponding aldehydes with a high selectivity (> 99%)
within 4 hours of illumination. We attribute this to the electron-
rich conjugated aromatic rings, which may lead to stronger
14]
adsorption on the catalyst surface.[1d,
We note that no
formation of deep oxidation products has been observed for all
cases (i.e., no carboxylic acids, CO, or CO2, Figure S5 in
Supporting Information), revealing the feasibility of the
Bi24O31Br10(OH)δ photocatalyst for practical applications.
Nevertheless, quantitative UV-vis spectrometry analysis has
also confirmed that benzaldehyde is the main product (yield >
96%) in photocatalytic benzyl alcohol conversion (Figure S6 in
Supporting Information).
We have further evaluated a set of Bi-relevant materials
without surface basicity (i.e., BiOBr, Bi2WO6, BiVO4, Bi2O3) for
the photo-oxidation of 1-octanol (Fig. 2a). All these materials
show very poor performance. The CO2 temperature
programmed desorption (TPD) confirms that only the
Bi24O31Br10(OH)δ exhibits distinct CO2 desorption peaks covering
the low-medium temperature regions, which correspond to weak
and medium basic features (Figure S7 in Supporting
Information). Since the basicity of the reaction system has a vital
effect on the activity in thermal catalytic alcohol oxidation,[15] we
have employed isopropanol (IPA) as the model substrate to
examine the external (pH of the solution) and internal (acid-base
properties of the material) basicity on the performance of the
Bi24O31Br10(OH)δ photocatalyst. As shown in Figure 2b, the
production rate of acetone decreases dramatically under acidic
conditions (pH 5, 2 µmol·h-1) compared to that of under neutral
conditions (13 µmol·h-1). The generation rate of acetone is
significantly enhanced by increasing the pH from 7 to 12.8 (47
µmol·h-1), while a further increase of the pH does not lead to
further improvement. The acid treated Bi24O31Br10(OH)δ shows
almost no activity for IPA oxidation under neutral conditions.
Therefore, we consider that the basicity from either the external
solution or the Bi24O31Br10(OH)δ photocatalyst is essential in
boosting the photo-oxidation of alcohols.
Figure 2. a) Photocatalytic performances of Bi-relevant photocatalysts for the
oxidation of 1-octanol. Reaction conditions: 50 mg catalyst in 10 mL
acetonitrile in 1 bar air at RT under 450 nm irradiation for 24 h (30 mW·cm-2).
b) Photocatalytic performance of Bi24O31Br10(OH)δ for the oxidation of 20 mL
IPA in 1 bar O2 at different pH under 450 nm irradiation (1 mW·cm-2). The pH
was adjusted by KOH and formic acid. The performance of acid-treated
Bi24O31Br10(OH)δ is also plotted for comparison (blue bar). c) Action spectrum
of Bi24O31Br10(OH)δ for the oxidation of IPA. Reaction conditions: 50 mg
catalyst in 10 mL 0.06 M KOH isopropanol (pH = 12.8) in 1 bar O2 at RT under
450 nm irradiation for 3 hours (1 mW·cm-2). d) Reusability analysis of
Bi24O31Br10(OH)δ for the oxidation of benzyl alcohol to benzaldehyde. Reaction
conditions: 8 mM reactant and 50 mg catalyst in 10 mL acetonitrile in air at RT
under 450 nm (0.03 W·cm-2) irradiation for 4 hours.
We also noticed that although O2 is necessary for completing
the catalytic cycle of the alcohol oxidation, it is not essential to
initiate the alcohol dehydrogenation process. When
photocatalytic IPA conversion was performed under anaerobic
conditions (1 bar Ar), the yellow catalyst turned black with a slow
formation of detectable acetone (Supporting Information, Figure
S8 and Table S1). The acetone production rate recovered to
normal under anaerobic conditions with the addition of
benzoquinone, which is used as electron and hydrogen acceptor
(Supporting Information, Table S1).
To understand the reaction mechanism and the nature of
active sites on the Bi24O31Br10(OH)δ photocatalyst, we have
further performed in-situ diffuse reflectance infrared Fourier
transform spectroscopy (DRIFT) analysis using deuterated
methanol (CD3OD) as probing molecule (Figure S9 in the
The quantum efficiency (QE) action spectrum for IPA
oxidation under optimal conditions is presented in Figure 2c (pH
= 12.8, 1 bar O2). Note the photocatalytic reaction system is
operated in the ‘‘catalyst saturated condition’’, in which a low
light intensity (1 mW·cm-2) and high catalyst concentration (5 g·L-
1) are applied to maximize light absorption to evaluate the true
QE of the photocatalyst (Figure S3b in Supporting
Information).[16] Remarkably, high QEs of 71% and 55% are
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10.1002/anie.201900773
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Supporting Information). A deuterated hydroxyl vibrational peak
is observed during CD3OD photo-oxidation under deaerated
conditions (2600 cm-1, Figure 3a and Figure S10 in the
Supporting Information). This suggests that the photogenerated
D atoms bond to the under-coordinated oxygen atoms of the
photocatalyst surface,[17] which are largely present in the bulk
Bi24O31Br10 material.[18] The intensity of this peak increases
gradually with increased irradiation time, resulting in
hydrogenation of the photocatalyst, during which its appearance
changes from yellow to black. XPS analysis of the radiated
Bi24O31Br10(OH)δ under deaerated conditions (benzyl alcohol as
reactant) shows that the peak position of Bi4f remains
unchanged, confirming that the photogenerated surface H atoms
are not directly bonded to Bi atoms (Figure S11 in the
Supporting Information). The O1s spectra reveal that the
concentration of OL decreased and converted to surface
adsorbed water after irradiation, as shown in Fig. 3(b).
Meanwhile the concentration of hydroxyls remains unchanged,
indicating that the surface basic sites are rather stable. This
information also agrees well with the in-situ DRIFT, confirming
that the photogenerated
H atoms are bonded to under-
coordinated O atoms, and can partially withdraw OL to initiate
alcohol oxidation even without the presence of molecular oxygen.
To complete the catalytic cycle, we have further analyzed
the gas phase products to probe the role of dioxygen by in-situ
mass spectrometry (MS) under 100 mbar O2, as demonstrated
in Fig. 3(c), 3(d) and Figure S12(a)-(d) in Supporting Information.
While solely gaseous H216O evolves when 16O2 is used as the
dioxygen source upon irradiation, both H216O and H218O evolve
when 18O2 is employed. In addition, 18O labeled benzaldehyde is
also observed (Figure S12e and S12f in Supporting Information).
The total amount of consumed O2 (0.67 and 0.64 μmol for 16O2
and 18O2) and generated water vapor (n[H216O] + n[H218O], 0.29
and 0.27 μmol for 16O2 and 18O2) are comparable for both
experiments, suggesting that the introduction of 18O2 shows
negligible effect to the reaction mechanisms. While a delayed O2
consumption is observed for both cases (~ 1 h after irradiation),
water forms immediately upon irradiation. These results reveal
Figure 3. a) In-situ DRIFT of Bi24O31Br10(OH)δ recorded during 450 nm
irradiation with the presence of CD3OD under deaerated conditions. b) XPS
analysis of O1s of the freshly prepared Bi24O31Br10(OH)δ (Fresh) and irradiated
Bi24O31Br10(OH)δ (Irr.) under deaerated conditions with the presence of benzyl
alcohol. c) and d) Evolution of gaseous water using 16O2 and 18O2 during
photocatalytic benzyl alcohol oxidation determined by in-situ MS. Reaction
conditions: 50 mg dried catalyst coated on quartz cell with 16 μL benzyl
alcohol, placed into a leak-tight reactor connected to MS. 450 nm irradiation
(500 mW) for 3 hours under 100 mbar O2. e) DFT calculation determined
optimized Bi24O31Br10(OH)δ surface structure and the formation energy of
oxygen vacancy from reactive lattice oxygen (indicated by arrows).
that
the
Bi24O31Br10(OH)δ first
initiates
the
photo-
In summary, we show that the solid base Bi24O31Br10(OH)δ
photocatalyst is capable of oxidizing a series of primary,
secondary and aromatic alcohols to their corresponding
aldehydes/ketones in air with excellent efficiency and selectivity.
Remarkably high quantum efficiencies are achieved under
visible light irradiation (71% and 55% at 410 and 450 nm,
respectively, for isopropanol oxidation). We propose that the
surface basic sites and active lattice oxygen of the
Bi24O31Br10(OH)δ photocatalyst are vital for efficient hydrogen
extraction from the alcohols. The synergy between base
catalysis and photocatalysis brings in an unprecedented
enhancement for selective alcohol oxidation under ambient
conditions and solar irradiation, which makes this cheap and
dehydrogenation of alcohols, forming surface adsorbed
hydrogen species on the photocatalyst. Then the OL of
Bi24O31Br10(OH)δ subsequently involves in the alcohol oxidation,
resulting the formation of water, aldehydes, and oxygen
vacancies (OV). Eventually the vacancies are healed by mild
oxidants (O2 or benzoquinone) to complete the photocatalytic
cycle (Scheme 1). The involvement of OL and the active sites
have been further calculated by density functional theory (DFT,
Figure S13 in Supporting Information). As demonstrated in Fig.
3(e), three different types of OL sites show similar minimum
formation energies of OV (~3 eV) on the optimized
Bi24O31Br10(OH)δ surface, suggesting the location of the active
sites. It is also worth noting that the formation energies of OV on
Bi24O31Br10(OH)δ surface is significantly lower compared to that
of on TiO2 surface (7.75 and 7.57 eV for rutile and anatase),[19]
indicating that the origin of the activity of the solid base
Bi24O31Br10(OH)δ.
robust photocatalyst
applications.
a promising candidate for practical
Acknowledgements
RS, YS and WH would like to thank the NSFC for financial
support (projects number: 21503257, 21601198, 51672018 and
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10.1002/anie.201900773
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COMMUNICATION
[14] M. J. Schultz, R. S. Adler, W. Zierkiewicz, T. Privalov, M. S. Sigman, J.
Am. Chem. Soc. 2005, 127, 8499-8507.
[15] a)S. Carrettin, P. McMorn, P. Johnston, K. Griffin, C. J. Kiely, G. J.
Hutchings, Phys. Chem. Chem. Phys. 2003, 5, 1329-1336; b)S.
Carrettin, P. McMorn, P. Johnston, K. Griffin, G. J. Hutchings, Chem.
Commun. 2002, 696-697.
[16] R. Su, R. Tiruvalam, A. J. Logsdail, Q. He, C. A. Downing, M. T. Jensen,
N. Dimitratos, L. Kesavan, P. P. Wells, R. Bechstein, H. H. Jensen, S.
Wendt, C. R. A. Catlow, C. J. Kiely, G. J. Hutchings, F. Besenbacher,
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[17] J. L. Davis, M. A. Barteau, Surf. Sci. 1990, 235, 235-248.
[18] U. Eggenweiler, E. Keller, V. Kramer, Acta Crystallogr., Sect. B: Struct.
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51472016). YD acknowledges the Sino-Danish Centre (SDC) for
a PhD scholarship. NL acknowledges the VILLUM Foundation
Young Investigator Programme (VKR023449) and the Danish
National Research Foundation (Carbon Dioxide Activation
Center, DNRF 118).
Keywords: Photo-oxidation • primary alcohols • visible light
photocatalysis • solid base • active lattice oxygen
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This article is protected by copyright. All rights reserved.

10.1002/anie.201900773
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Selective photooxidation of
alcohols: The Bi24O31Br10(OH)δ
photocatalyst is very efficient in
selective oxidation of various aliphatic
and aromatic alcohols to their
corresponding aldehydes/ketones
under visible light irradiation in
ambient conditions. The outstanding
performance is associated with
surface basic sites and active lattice
oxygen, which boost the
Y. Dai, P. Ren, Y. Li, D. Lv, Y. Shen, Y.
Li, H. Niemantsverdriet, F. Besenbacher,
H. Xiang, W. Hao, N. Lock, X. Wen, J. P.
Lewis, R. Su*
Page No. – Page No.
Solid Base Bi24O31Br10(OH)δ with
Active Lattice Oxygen for Efficient
Photo-oxidation of Primary Alcohols
to Aldehydes
dehydrogenation step in the photo-
oxidation of alcohols. (see picture).
Keywords
Photo-oxidation; primary alcohols; visible light photocatalysis; solid base; active lattice oxygen
This article is protected by copyright. All rights reserved.