Photocatalytic Upgrading of Lignin Oil to Diesel Precursors and Hydrogen

Article abstract of DOI:10.1002/anie.202105692

Producing renewable biofuels from biomass is a promising way to meet future energy demand. Here, we demonstrated a lignin to diesel route via dimerization of the lignin oil followed by hydrodeoxygenation. The lignin oil undergoes C?C bond dehydrogenative coupling over Au/CdS photocatalyst under visible light irradiation, co-generating diesel precursors and hydrogen. The Au nanoparticles loaded on CdS can effectively restrain the recombination of photogenerated electrons and holes, thus improving the efficiency of the dimerization reaction. About 2.4 mmol g_catal^?1 h^?1 dimers and 1.6 mmol g_catal^?1 h^?1 H₂ were generated over Au/CdS, which is about 12 and 6.5 times over CdS, respectively. The diesel precursors are finally converted into C16–C18 cycloalkanes or aromatics via hydrodeoxygenation reaction using Pd/C or porous CoMoS catalyst, respectively. The conversion of pine sawdust to diesel was performed to demonstrate the feasibility of the lignin-to-diesel route.

Full text of DOI:10.1002/anie.202105692

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Accepted Article
Title: Photocatalytic upgrading of lignin oil to diesel precursor and
hydrogen
Authors: Zhaolin Dou, Zhe Zhang, Hongru Zhou, and Min Wang
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10.1002/anie.202105692
Angewandte Chemie International Edition
RESEARCH ARTICLE
Photocatalytic upgrading of lignin oil to diesel precursor and
hydrogen
Zhaolin Dou, Zhe Zhang, Hongru Zhou, Min Wang*
Dr. M. Wang, Dr. Z. Zhang, Z. Dou, H. Zhou
Zhang Dayu School of Chemistry, Dalian University of Technology
Dalian 116024, Liaoning, China
E-mail: wangmin@dlut.edu.cn
Supporting information for this article is given via a link at the end of the document.
Abstract: Producing renewable biofuels from biomass is
a
and aromatics which possess higher energy density.[18]
Hydrodeoxygenation (HDO) catalysts and processes have been
extensively studied to upgrade the phenolics to hydrocarbons
(C8-C9) with gasoline range hydrocarbons.[16, 19-25]
In this study, we propose the conversion of lignin oils to
diesel fuels. The lignin oils are mostly composed of C8-C9
phenolics. To achieve this lignin to diesel route, the carbon chain
promising way to meet future energy demand. Here, we
demonstrated a lignin to diesel route via dimerization of the lignin oil
followed by hydrodeoxygenation. The lignin oil undergoes C−C bond
dehydrogenative coupling over Au/CdS photocatalyst under visible
light irradiation, co-generating diesel precursors and hydrogen. The
Au nanoparticles loaded on CdS can effectively restrain the
recombination of photogenerated electrons and holes, thus
improving the efficiency of the dimerization reaction. About 2.4 mmol
must be lengthened to
a
certain degree before
hydrodeoxygenation to alkanes. Dimerization of lignin-derived
phenolics via C−C bond coupling is a good way to produce C16-
C18 alkane precursors and simultaneously produce hydrogen,
while the key is the C−H bond homo-cleavage to form carbon-
centered radicals. Dehydrogenative coupling reaction is an
effective method for the formation of C-C bond from C-H bond,
while it is thermodynamically unfavorable and generally needs
the use of oxidant as the driving force.[26-27]
-1
-1
gcatal h-1 dimers and 1.6 mmol gcatal h-1 H2 were generated over
Au/CdS, which is about 12 times and 6.5 times over CdS,
respectively. The diesel precursors are finally converted into C16-
C18 cycloalkanes or aromatics via hydrodeoxygenation reaction
using Pd/C or porous CoMoS catalyst, respectively. The conversion
of pine sawdust to diesel was performed to demonstrate the
feasibility of the lignin-to-diesel route.
Photocatalytic valorization of biomass feedstocks
represents a new and promising approach to achieve a higher
grade of sustainability in chemical processes.[28] Various
photoreactions and photocatalysts have been developed for
Introduction
biomass conversion to produce hydrogen,[29] liquid fuels,[30-31]
and chemicals.[32-33]
,
Utilization of renewable biomass resource to produce fuels and
chemicals
Lignocellulose, composed of cellulose, hemicellulose, and lignin,
is the largest abundant and inedible bioresource and
have
aroused
increasing
investigation.[1-3]
a
promising feedstock to produce biofuels and biochemicals.
However, compared with cellulose and hemicellulose, lignin is
the least susceptible to chemical and biotransformation
techniques and becomes the bottleneck for the biorefinery
process. Most biorefinery processes currently only utilized the
carbohydrate fractions (cellulose and hemicellulose), while
leaving lignin underutilized. The worldwide lignin production from
the paper industry is about 50-70 million tons annually, and
approximately 98% of that is simply burned to generate heat.[4]
Thus, efficient valorization of lignin into value-added chemicals
or fuels is crucial to make the industrial-scale biorefinery plants
cost-competitive.
Great research has been devoted to depolymerizing lignin
to a mixture of phenolics (lignin oil) followed by sequential
upgrading to useful chemicals and liquid fuels.[5-7] Some value-
added chemicals, such as PTA,[8] phenol,[9-13] and, nitrogen-
containing compounds,[14-17] were usefully produced from lignin-
derived phenolics. Direct upgrading lignin oil to biofuel is another
promising route and benefited from the no necessary pre-
separation of the lignin oil feedstock and post-separation of
product from the reaction mixture. Moreover, compared with
carbohydrate-derived biofuels (ethanol, chain alkanes, and so
on), lignin oils as feedstock can potentially produce cycloalkanes
Scheme 1. The scheme for upgrading of lignin oil.
Herein, we report the photocatalytic upgrading of lignin oil
to diesel precursor. We develop a photocatalytic method to
activate the C−H bond, thus realizing the C−C bond coupling
(Scheme 1). The dimerization to diesels processors is achieved
via visible-light-driven benzylic C−C bond coupling over Au/CdS
photocatalyst at room temperature along with co-production of
H2. After HDO, a complex mixture of cycloalkanes or aromatics
with a C16-C18 carbon chain are obtained depending on the
hydrodeoxygenation process, which can be potential used as
diesel.
Results and Discussion
1
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10.1002/anie.202105692
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RESEARCH ARTICLE
The crystalline phases of CdS and Au/CdS were investigated by
X-ray diffraction (XRD). As shown in Figure S1, both CdS and
Au/CdS show the characteristic diffraction peaks of hexagonal
phases CdS.[34] But no diffraction peaks assigned to Au are
observed in Au/CdS, which is due to its low content and high
dispersity.[35] As shown in higher resolution transmittance
microscopy (HR-TEM) image (Figure 1 a), Au particles with the
size of 0.8-2.4 nm (Figure S2) are highly dispersed on CdS
nanorod, and the lattice space of CdS (002) and Au (200) plane
An etherified lignin-derived compound, 4-ethyl-1-
methoxybenzene, was employed as
a probe molecule to
investigate the dehydrocoupling reaction. The reactions require
simultaneous cleavage of the inert C−H bond and release of H2.
There are four kinds of C−H bonds in the molecule: sp2 C−H,
sp3 C−H in the methyl group, sp3 C−H in the methoxyl group,
and benzylic sp3 C−H. Among these C−H bonds, the benzylic
C−H is the weakest one with bond dissociating energy (BDE) of
3.77 eV and is probably the dehydrocoupling reaction site
(Figure 2 a). The reaction is thermodynamically unfavorable with
positive reaction energy of 0.32-0.34 eV. Therefore, the
dehydrocoupling reaction is difficult to occur under thermal
conditions. We then performed the photocatalytic coupling of 4-
ethyl-1-methoxybenzene using some typical photocatalyst under
visible light (455 nm LEDs) irradiation in MeCN solvent at room
temperature (Figure S4 a). Most of the widely used catalysts,
such as Pd/TiO2, Ru/TiO2, Cu2O, CeO2, Bi2WO6, ZnS, In2S3,
were inactive for this reaction. CdS showed some activity for the
C–C bond coupling reactions, producing dimers and H2. The
dimers are formed via the benzylic carbon coupling. Although
CdS itself showed lower activity, immobilization of gold on CdS
significantly increased the dimer yields to 76 wt% in 6 h. The
yield of the dimer was increased to 83 wt% in 24 h (Table 1).
CdS with different morphology were investigated toward the
coupling reaction, and the CdS nanorod shows the highest
reaction activity (Figure S5). Ru/ZnIn2S4 was previously used for
the dehydrocoupling of methylfurans[30] and shows a relatively
lower dimers yield (28 wt%) than that over Au/CdS (Figure S4 a).
The Au/CdS were reused four times with some loss of activity
(Figure S6). The solvent shows a significant effect on the C−C
bond coupling reaction. Acetonitrile shows the best performance
among the tested organic solvents (Figure S4 b). The reaction
could be also carried out in solvent-free condition, generating
were observed (Figure
composition and chemical states of Au/CdS were analyzed by X-
ray photoelectron spectroscopy (XPS). In Figure 1 c, the double
1
b).[36-37] The surface elemental
peaks located at 84.3 eV and 88 eV can be assigned to metallic
[37-38]
Au 4f7/2 and 4f5/2
.
The Cd 3d of Au/CdS shows the
characteristic double peaks at 405.3 eV for Cd2+ 3d5/2 and 412
eV for Cd2+ 3d3/2 (Figure 1 d).[39] The double peaks of S 2p3/2 and
2p1/2 can be observed at 161.7 eV and 162.9 eV (Figure 1 e).[40]
Compared with CdS, the S 2p and Cd 3d peaks of Au/CdS are
shifted to high energy due to strong interaction between Au and
CdS.[41] The VB position derived from VB-XPS is 1.28 and 1.8
eV for CdS and Au/CdS, respectively (Figure S3).
Photoelectric properties of the catalysts were investigated
by UV-vis diffuse reflectance spectra (UV-vis DRS),
photoluminescence (PL), and surface photovoltage (SPV). The
introduction of gold increases the absorbance of visible light and
decreases band-gap energy from 2.4 eV to 2.36 eV (Figure 1f).
The immobilization of gold on CdS improves photoinduced
carrier separation as demonstrated by PL and SPV
characterizations. Compared with CdS, Au/CdS exhibits a much
weaker PL intensity (Figure 1 g), because the Au restrains the
recombination of photogenerated electrons and holes by forming
the Schottky barrier at Au and CdS interface.[42] SPV is defined
as the illumination-induced changes of the surface potential. As
shown in Figure 1 h, the SPV signal of Au/CdS is much stronger
than that of CdS, implying the electron-collecting effect and
contributing to efficient charge carrier separation.[43]
-1
-1
0.14 mmol gcatal h-1 of dimers and 0.13 mmol gcatal h-1 of H2.
Scale-up by 10 times of the substrate with a higher power light
source (60 W), the generation of dimers and H2 are nearly
-1
linearly increased with the reaction time. About 2.4 mmol gcatal
h-1 of dimers and 1.6 mmol gcatal h-1 of H2 was generated over
a
b
-1
0.341 nm
CdS (002)
Au/CdS, which is about 12 times and 6.5 times over CdS,
respectively (Figure 2). The yield of dimers reaches 42 wt% in
the scale-up reaction in 12 h. Notably, 5.9% apparent quantum
yield (AQY) is obtained over Au/CdS, which is approximately 8
times over CdS (0.75% of AQY).
0.205 nm
Au (200)
20 nm
10 nm
20 nm
S 2p3/2
c
d
e
Au 4f7/2
Cd 3d5/2
S 2p
S 2p1/2
Au 4f
Cd 3d
Cd 3d3/2
Au 4f5/2
Au/CdS
Au/CdS
CdS
CdS
100
95
90
85
80
420
415
410
405
400
164 163 162 161 160
Binding Energy (eV)
Binding Energy (eV)
Binding Energy (eV)
f
g
h
CdS
Au/CdS
Au/CdS
CdS
CdS
2.36 eV
2.4 eV
Au/CdS
2.1
2.4
2.7
3.0
3.3
400
450
500
550
600
300 350 400 450 500 550 600
Wavelength (nm)
hv (eV)
Wavelength (nm)
Figure 2. Time-on-course process of the production over Au/CdS and CdS. a
Figure 1. Characterization of the catalysts. a, b HR-TEM images of Au/CdS. c-
e XPS spectra. f Plots of (αһν)2 versus photon energy (һν), g PL spectra, h
SPV spectra.
The equation of dehydrocoupling reaction. b Dimers. c H2. Reaction
conditions: 1 mL of 4-ethyl-1-methoxybenzene, 50 mg of Au/CdS, 10 mL of
CH3CN, 455 nm LED (60 W) irradiation, Ar atmosphere.
2
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10.1002/anie.202105692
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RESEARCH ARTICLE
Various lignin-derived phenolics, such as 4-ethylphenol, 4-
propylphenol, 2-methoxy-4-propylphenol and their etherified
compounds, such as 1-methoxy-4-ethylbenzene, 1-methoxyl-4-
propylbenzene, 1, 2-dimethoxy-4-ethylbenzene, and 1, 2-
dimethoxy-4-propylbenzene, all facially underwent self-coupling
To demonstrate the feasibility of this method to produce
diesel fuels, we further investigated the hydrodeoxygenation of
the dimers to alkanes. Pd/C is effective for the
hydrodeoxygenation of the dimers to saturated cyclic alkanes.
Figure S7 b shows the GC spectrum of hydrogenation of the
dimers over Pd/C. A mixture of saturated cyclic alkanes with
C16-C18 was produced with a total yield of 58 wt% (theoretical
maximum yield: 77 wt%). The composition of the product can be
tuned when using a different catalyst. We prepared a porous
CoMoS-P catalyst for hydrodeoxygenation, which prefers to form
aromatics. As shown in the GC spectrum (Figure S7 c), a
mixture of aromatics with C16-C18 carbon chains was produced
over CoMoS-P, and the total yield of the aromatics is 53 wt%
(theoretical maximum yield: 74 wt%).
-1
to form dimers with 56-83 wt% yield and 6-11 mmol gcatal of H2
(Table 1). Depolymerization of lignin will produce a mixture of
various aromatics. We then investigated the cross-coupling of
aromatic mixtures. A mixture of 1-methoxy-4-ethylbenzene, 1-
methoxyl-4-propylbenzene and 1, 2-dimethoxy-4-propylbenzene
with a molar ratio of 1:1:1 was used to mimic the lignin oil. As
shown in the gas chromatography (GC) spectra (Figure S7 a),
both homo-coupling and cross-coupling reactions took place and
produced eight dimers with a total 78 wt% yields along with 8.6
mmol gcatal-1 of H2 in 48 h.
Finally, we showed an example to prove the feasibility of
the present method for the conversion of raw biomass to diesel
(Figure 3). The pine sawdust was employed as the feedstock.
Firstly, the pine sawdust was hydrogenated over Ru/C in
methanol solvent at 250 °C. After filtration of catalyst and
evaporation of methanol solvent, the residues underwent
etherification with dimethyl carbonate. 1,2-dimethoxy-4-
ethylbenzene and 1,2-dimethoxy-4-propylbenzene were the
major products (Figure S8 a). The as-obtained lignin oil further
underwent photocatalytic coupling reaction under 455 LED
irradiation and produced dimers (Figure S8 b) with 76 wt% yield
(based on lignin oil) and H2 (4.6 mmol per gram of lignin oil). The
as-obtained dimers were hydrogenated over Pd/C and CoMoS-P
catalyst at 300 ºC in 3MPa H2, generating 28 wt% C16-C18
cycloalkane (Figure S8 c) and 38 wt% aromatics (Figure S8 d),
respectively. Compared with the pure lignin models, the
hydrodeoxygenation of this crude lignin oil-derived dimers is
relatively lower probably due to the presence of contaminants in
the lignin oil.
Table 1. Substrate scope of dehydrocoupling reaction.
[b]
Entry
1
Substrate
Product
Yield[a]
83
H2
11
2
76
10
3
4
71
69
10
9
The reaction mechanism was studied using a 2,2,6,6-
tetramethylpiperidine-1-oxyl
(TEMPO),
styrene
trapping
experiment, and in situ electron spin resonance (ESR) using
DMPO as a spin-trapping reagent. The addition of radical-
trapping reagent TEMPO nearly completely prohibited the
formation of C−C coupling products (Figure 4 a), suggesting a
radical mechanism. The occurrence of C−H bond activation was
verified by the formation of TEMPOH and a small amount of H2
(0.5 mmol gcatal−1). When styrene was used as the radical-
trapping reagent, an addition coupling product was generated
(Figure 4 b), directly indicating that the benzylic carbon radical is
formed during photo-irradiation. The ESR result further reveals
the generation of benzylic carbon radical on Au/CdS catalyst
(Figure S9). The formation of benzylic carbon radical is strongly
affected by the C−H BDE. The dimers yields are related to the
BDE, which is decreased with the increase of the BDE (Figure 4
c). The lignin-derived aromatic monomers possess relatively low
BED due to the presence of electron-donating groups and hence
could undergo dimerization reaction well.
5
6
69
59
11
6
7
57
11
Reaction conditions: 0.1 mmol of substrate, 5 mg of Au/CdS, 1 mL of CH3CN,
455 nm LED (18 W) irradiation for 24 h, Ar atmosphere. [a] Yield of product:
-1
wt%. [b] H2 production: mmol gcatal
.
3
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10.1002/anie.202105692
Angewandte Chemie International Edition
RESEARCH ARTICLE
Figure 3. The process of raw lignin to C16-C18 cyclic alkanes and aromatics.
100
80
60
40
20
0
10
8
a
b
Dimers
H2
No additives
6
4
Styrene
2
TEMPO
0
2
3
4
12
13
14
15
Retention time (min)
H2
c
d
100
80
60
40
20
0
1
4
2
3
6
Au
1
e- e-
-0.5 V
5
H+
+
2
CdS
1.86 V
5
3
9
8
7
h+ h+
6
8
4
7
9
10
10
3.75 3.80 3.85 3.90 3.95 4.00
BDE of C-H (eV)
Figure 4. Reaction mechanism study. a Reactivity of dehydrocoupling reaction in the presence of styrene and TEMPO. Reaction conditions: 0.1 mmol of 4-ethyl-
1-methoxybenzene, 0.2 mmol of styrene or TEMPO, 5 mg of Au/CdS, 1 mL of CH3CN, 455 nm LED (18 W) irradiation for 6 h, Ar atmosphere. b Typical GC
spectra of the reaction mixture in (a). c The effect of benzylic C-H BDE for the dehydrocoupling reaction. Reaction conditions: 0.1 mmol of substrate, 5 mg of
Au/CdS, 1 mL of CH3CN, 455 nm LED (18 W) irradiation for 6 h, Ar atmosphere. d Proposed reaction mechanism of photocatalytic dehydrocoupling of 4-ethyl-1-
methoxybenzene.
holes oxidize the benzylic C-H bond to afford carbon-centered
radicals which undergo C-C bond coupling to dimers. The
generated protons are reduced by the photogenerated electrons
in the CB to H2.
The proposed reaction mechanism is shown in Fig. 4d.
Au/CdS has a VB top potential of 1.86 V versus RHE (Figure
S10), which is larger than the oxidation potential (1.55 V) of 4-
ethyl-1-methoxybenzene (Figure S11). The photogenerated
4
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10.1002/anie.202105692
Angewandte Chemie International Edition
RESEARCH ARTICLE
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We reported a method to convert lignin oils to diesel. The lignin
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This work was supported by the National Natural Science
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Keywords: photocatalysis • lignin • diesel • C−C coupling •
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10.1002/anie.202105692
Angewandte Chemie International Edition
RESEARCH ARTICLE
Entry for the Table of Contents
Ru/C
C16-C18 cyclic hydrocarbons
C16-C18 aromatics
Lignin
Au/CdS
CoMoS-P
H2
Diesel precursors
solar driven coupling
hydrogenation
A lignin to diesel precursors route was achieved via solar driven coupling reaction over Au/CdS photocatalyst. The diesel precursors
can be further hydrogenated to C16-C18 cyclic hydrocarbons or aromatics over Ru/C or CoMoS-P, respectively.
6
This article is protected by copyright. All rights reserved.