pubs.acs.

org/EF Article

Lignin Catalytic Depolymerization for Guaiacols and Alkylphenols

over Co−Zr/Sepiolite under Supercritical Ethanol
Mingqiang Chen,* Zinan Zhou, Yishuang Wang,* Zheng Fang, Defang Liang, Longyang Li,
Haosheng Xin, Chang Li, Gang Yuan, and Jun Wang
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ABSTRACT: Lignin catalytic depolymerization (LCD) in supercritical

ethanol for the preparation of liquid fuels and phenolic monomers is
Downloaded via CHONNAM NATL UNIV on March 12, 2024 at 14:23:58 (UTC).

one of the promising strategies for the valorization of lignocellulosic

biomass. This paper reported sepiolite (SEP)-supported Co−Zr
catalysts (Co−Zr/SEP) with different Co/Zr ratios for LCD in
supercritical ethanol. The characterization results revealed that the
cobalt oxides interacted with the SEP framework to create abundant
pores, which increased the accessibility of the active sites with lignin
fragments. Furthermore, the Zr additive promoted the conversion of
Co(OH)2 to Co3O4 to increase Lewis acid sites (LAS) and oxygen
vacancies (VO), which could enhance the adsorption and stabilization of
reactive intermediates. Among the samples, 3Co1Zr/SEP exhibited the
superior surface area and the highest LAS and abundant VO. The
experimental results showed that the Co/Zr ratio significantly affected
the yields of liquid products and phenolic monomers, and 3Co1Zr/SEP achieved the outstanding liquid product yield (60.11%) and
the optimal yields of guaiacols (445.2 mg/g lignin) and alkylphenols (109.8 mg/g lignin) under the optimal reaction conditions.
Additionally, 3Co1Zr/SEP significantly reduced the apparent activation energy for breaking β-O-4 bonds to 71.46 from 89.94 kJ·
mol−1 over SEP by model experiments; furthermore, the possible reaction pathways of LCD over 3Co1Zr/SEP were proposed.

1. INTRODUCTION and 1,4-dioxane coupled with hydrogen pressures (2−4 MPa)

Lignin, as one of the abundant natural renewable resources, has
been extensively researched in the field of fabricating aromatic
products, biodegradable materials, and liquid fuels due to the
specificity of its composition and structure.1−3 It has been
found that lignin consists of coumarin (H), mustard alcohol
(S), and pineal (G) groups, which are randomly connected by
C−C/C−O bonds (4-O-5, α-O-4, β-O-4, β−β, β-1, etc.) to
form natural aromatic polymer compounds with complex
three-dimensional networks.4−8 In recent years, on the
strength of the structural characteristics of lignin, it has been
extensively demonstrated that lignin catalytic depolymerization
(LCD) for liquid fuels and cooperative production of phenolic
monomers is one of the promising methods for highly efficient
utilization of lignin.9,10
However, it had been found that the produced highly
reactive intermediates during the LCD process underwent an
irreversible condensation reaction and formed abundant coke,
which restricts the advancement of LCD technology.11,12 It has
been demonstrated that LCD under a special solvent system
and a reducing atmosphere could inhibit coke and increase the
HHV (higher heating value) of liquid products and the
selectivities of different monomers.13−16 Li et al.17−20
developed an advanced solvent system consisting of methanol
to achieve the lignin depolymerization into liquid fuels and
significantly inhibit the coke formation. Shu et al.21 proposed a
solvent system of metal chloride cooperated with methanol to
achieve lignin depolymerization with controllable product
distribution under a hydrogen pressure of 4 MPa. This catalytic
system suppressed the polymerization of ester structures in
lignin and improved the conversion efficiency of lignin to fuel.
In addition, some other solvents including n-hexane,
diisopropyl ether, ethyl acetate, methanol, and acetone
cooperated with hydrogen pressure (3−5 MPa) were
developed for lignin depolymerization.22−24 Although the
HHV of the liquid product or monomer selectivity was clearly
improved by employing the complex solvent systems and the
high hydrogen pressure, the high cost of solvent and
downstream product separation and the urgent need for
Received: November 22, 2023
Revised: January 30, 2024
Accepted: January 30, 2024
Published: February 13, 2024

© 2024 American Chemical Society https://doi.org/10.1021/acs.energyfuels.3c04637

4256 Energy Fuels 2024, 38, 4256−4272
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Scheme 1. Preparation of the SEP Precursor (a), Synthetic Process of Co−Zr/SEP (b), and Lignin Depolymerization Process
(c)
delicate catalysts that can efficiently activate hydrogen become
a great challenge.
Recently, it has been found that depolymerization of lignin
in the ethanol system, especially supercritical ethanol, to
replace the molecular hydrogen source is among the most
competent methods for producing liquid fuels and aromatic
products.25−32 It has been demonstrated that supercritical
ethanol not only could enhance heat transfer and improve the
solubility of lignin/intermediates but could also act as a
nucleophile to break ether bonds in lignin.26−28 Huang et al.29
investigated the LCD using Cu−Mg−Al mixed oxide catalysts
in supercritical ethanol and confirmed that the hydrogen
produced from ethanol was involved in breaking the lignin C−
O bonds and the deoxygenation reaction of monomers and
oligomers. Although the LCD technology under supercritical
ethanol can inhibit the char formation and realize the
hydrogenation of the reaction process, improving the lignin
depolymerization efficiency and the selectivity of special
monomers is still one of the research emphases of lignin
valorization. It has been widely accepted that the design and
preparation of advanced catalysts is an effective measure to
realize this process. Tran et al.31 designed copper supported on
the chromium-based metal−organic framework (MOF) (Cu@
MIL-101(Cr)) for LCD in supercritical ethanol and found that
the MOF framework increased the Cu particle dispersion and
stabilized the Cu sites that could induce the selective breaking
of ether bonds in lignin. This resulted in the concentration of
guaiacols obtaining a yield of 38.5%. In our previous work,33,34
the catalysts of Mn-modified Mo/sepiolite (SEP) were
synthesized and used for LCD in supercritical ethanol.
Different from more than 20 alkylation products produced
by Mo/SEP in supercritical ethanol for LCD, the inclusion of
manganese enhanced the proficiency to selectively cleave the
β-O-4 bonds and repressed the isomerization and alkylation
processes of the reactive intermediates, resulting in reduction
of the production of alkylation products and the enrichment of
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phenols, whose selectivity reached to 85.61%. Therefore, it can
be found that the option of suitable active components
particularly metals/metallic oxides and coupling them with
unique supports is considered as very important for designing
and preparing advanced catalysts for LCD.
Non-noble-metal-based catalysts including Ni-, 3 0
W-,35,36,46,54 Co-,19,40,41 and Mo-based catalysts5,32−34,53 have
been utilized in lignin conversion owing to their superior
breaking capability for C−C/C−O of lignin and hydro-
genation function. Especially, the phase of Co3O4 with a spinel
structure in Co-based catalysts has multiple functions of Lewis
acid sites (LAS) derived from the Co2+ atoms located in the
tetrahedron and Brønsted acid sites (BAS) originated from the
Co3+ atoms located in the octahedron.37,38 In addition, the
Co2+ and Co3+ atoms of Co3O4 could be substituted by other
atoms to generate more oxygen vacancies (VO).57 It is
generally accepted that the acidic sites (LAS and BAS) and
VO could improve the C−O bond breaking and hydrogenation
ability.39,40 Qi et al.41 used Ni doping into Co3O4 to tailor the
NixCo3−xO4 catalysts' Brønsted and Lewis acid centers and
employed the as-prepared catalysts into LCD. It was found
that the Ni species optimized the synergistic effect between
acid centers including BAS and LAS and active sites to
promote the lignin cleavage and the excellent selectivity to
aromatic monomers (up to 90.30 wt %). It can be found that
the formation of Vo in Co-based catalysts could activate the
lignin C−O bonds and reduce the dissociation energy of C−O
bonds, which led to further deoxygenation and hydrogenation.
It has been demonstrated that addition of ZrO2 with high
oxygen storage capacity into metal-based catalysts could
enhance the generation of abundant VO to improve the
catalytic performance.42−46 Garciá et al.46 reported the
catalytic production of γ-valerolactone from furfural over
SnZr/Y catalysts with different ratios of Sn and Zr and found
that the formed Zr−O−Sn increased the active species
dispersity and the addition of Zr gave rise to more BAS and
https://doi.org/10.1021/acs.energyfuels.3c04637
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LAS. However, the use of Co−Zr-based catalysts for exploiting
LCD has been little studied to our knowledge.
In addition to this, the selection of excellent support
materials could optimize catalytic activity and increase the
service life of catalysts. Natural clay sepiolite (SEP) has a
special nanolayered structure, and its abundant pore structure
could anchor and disperse the active metals.33,34 Based on its
structural characteristics, the SEP as a support or catalytic
component had been widely applied into various catalytic
reactions.47−49 In addition, a series of SEP-supported metal-
based catalysts in our previous reports had been prepared and
used for LCD.33−35,50
In this paper, for further improving the yield of the phenolic
monomer, SEP-supported Co−Zr catalysts (Co−Zr/SEP)
with different mass ratios of Co and Zr were prepared for
LCD in supercritical ethanol. The catalysts that had been
prepared underwent characterization by using various methods
such as XRD, HRTEM, FTIR, Raman analysis, XPS, EPR, Py-
IR, and NH3-TPD to reveal the effect of Co/Zr mass ratios on
the structural properties of as-prepared catalysts. In addition,
elemental analysis, GC-MS, and 2D-HSQC NMR were used to
analyze the liquid-phase products. Model substances with
characteristic lignin structures were utilized to elucidate the
possible reaction mechanism and pathways for LCD.
2. EXPERIMENTAL SECTION
2.1. Materials. Sepiolite (SEP) was purchased from Shanlin Shiyu
Mineral Products Co., Ltd. (Hunan, China). Kraft lignin (Indulin AT)
was procured from Mead Westvaco (Shanghai, China). The solvents
and chemical reagents utilized in this study were procured from
Sinopharm Chemical Reagent Co., Ltd. (located in Shanghai, China),
and all solvents and chemical reagents were of AR (analytical reagent)
purity. Co(NO3)2·6H2O (cobalt nitrate hexahydrate) and Zr(NO3)4·
5H2O (zirconium nitrate pentahydrate) were employed as the
precursors of Co and Zr, respectively. 2-Phenoxy-1-phenylethanol
(PP) was used in the model experiments.
2.2. Catalyst Preparation. Initially, 20 g of SEP was treated in
100 mL of 5 mol/L NaOH solution at 60 °C for 2 h. It was then
transferred to a hydrothermal synthesis reactor and maintained at 180
°C for 12 h. The solid product obtained was washed with deionized
water multiple times before being dried overnight at 150 °C. The
recovered solids were subsequently calcined in an air atmosphere at
500 °C with a heating ramp of 4 °C/min over 4 h to obtain the
purified SEP. The preparation procedure can be observed in Scheme
1a.
The catalysts comprising Co−Zr/SEP were created using the
impregnation−precipitation technique. The diagram detailing the
process is shown in Scheme 1b. Typically, the predetermined amount
of Co(NO3)2·6H2O was dissolved in 50 mL of deionized water, and 1
g of purified SEP was added. The mixture was then stirred for 2 h at
room temperature. Then, a certain amount of urea (generally the
molar ratio of Co(NO3)2·6H2O and urea was 0.5) as the precipitant
was added into above turbid liquid and continuously stirred for 8 h at
90 °C to form the pink suspension. Subsequently, the above pink
suspension was then mixed with Zr(NO3)4 solution (the predeter-
mined amount of Zr(NO3)4·5H2O was dissolved in 50 mL of
deionized water) and agitated for 8 h at 60 °C. Following this, the
solution underwent dehydration through an evaporation process at 90
°C and was left to dry overnight at 105 °C. The resulting solid
material was subjected to calcination at 500 °C (with a heating ramp
of 4 °C/min) for 4 h in stagnant air to produce the Co−Zr/SEP
catalyst. Herein, the metal content of Co+Zr was fixed to 20 wt %, the
mass ratios of Co/Zr were 3/1, 1/1, and 1/3, and the corresponding
catalysts were named as 3Co1Zr/SEP, 1Co1Zr/SEP, and 1Co3Zr/
SEP.
Co/SEP was prepared employing the precipitation method. As in
the preparation process of Co−Zr/SEP described above, the resulting
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pink suspension was filtered, washed using deionized water, and dried
at 105 °C for 12 h. The Co/SEP catalyst was obtained by calcining
the solid at 500 °C for 4 h under static air with a heating ramp of 4
°C/min. The content of Co was fixed at 20 wt % in this process.
Zr/SEP was prepared employing the impregnation method.
Typically, the predetermined amount of Zr(NO3)4·5H2O was
dissolved in 50 mL of deionized water. Then, 1 g of purified SEP
was added, and the mixture was stirred for 8 h at 60 °C. After that, the
mixture was dehumidified by an evaporation process at 90 °C and
dried at 105 °C for 12 h. The Zr/SEP catalyst was obtained by
calcining the solid at 500 °C for 4 h under static air with a heating
ramp of 4 °C/min. The content of Zr was fixed at 20 wt % in this
process.
2.3. Catalyst Characterization. N2 adsorption−desorption
analysis was conducted using a BELSORP-mini II surface area
analyzer (made in Japan) at a temperature of −196 °C. The specific
surface area was calculated employing the Brunauer−Emmet−Teller
(BET) technique, while the pore volume and pore size distribution
were measured via the Barrett−Joyner−Halenda (BJH) method.
The actual contents of Si, Al, Co, and Zr from the catalysts were
calculated by inductively coupled plasma-optical emission spectrom-
etry (ICP-OES) on an Agilent ICP-OES 5110 (USA).
X-ray diffraction was carried out to analyze the crystal phases of the
catalysts prepared using a Rigaku Corporation SmartLab (3 kW) X-
ray diffractometer from Japan. This used Co Kα as the radiation
source, set at 40 kV and 40 mA, with λ = 0.17902 nm and a scanning
step of 0.02° for 2θ = 5−70°.
FTIR spectra of the samples were acquired using a Nicolet iS50
spectrometer (USA). FTIR spectroscopy was conducted within the
wavenumber range of 4000−400 cm−1. Prior to measurement, all
samples were uniformly diluted in spectroscopic-grade KBr powder
(4−8 wt % in KBr).
Raman spectra of samples were recorded by a Renishaw inVia
(UK) instrument with a 532 nm laser (Ar+) at a maximum power of
100 mW.
X-ray photoelectron spectroscopy (XPS) was utilized to investigate
the states of elements in the samples using a Thermo Fisher
ESCALAB 250Xi X-ray photoelectron spectrometer (UK), with Al
Kα (1486.68 eV) as the photon source.
The electron paramagnetic resonance (EPR) of the samples was
measured by using a Bruker A300 EPR spectrometer (Germany).
FEI Tecnai G2 F20 (USA) transmission electron microscopy
(TEM), high-resolution transmission electron microscopy
(HRTEM), and TEM-EDX were used to examine the microstructure
and distribution of elements of the samples at an accelerating voltage
of 200 kV.
The reduction process of the catalysts was analyzed using hydrogen
temperature-programmed reduction (H2-TPR) analysis on an
Autochem II 2920 manufactured in the USA. Hydrogen consumption
was measured with a thermal conductivity detector (TCD), and the
sample temperature was ramped from 10 to 800 °C at a rate of 10
°C/min.
The acid properties of the sample surface were detected using
ammonia temperature-programmed desorption (NH3-TPD) on an
Autochem II 2920 (USA). Before chemisorption, the samples
underwent pretreatment in helium at 200 °C for 1 h. Following
this, the temperature was brought down to 50 °C in helium, and a
mixture flow of 5% NH3/He was injected until the surface of the
samples became saturated. The sample was subjected to a stream of
helium at a flow rate of 30 mL min−1 and maintained at 120 °C for an
hour. The desorption process for NH3 was carried out by gradually
increasing the temperature to 700 °C at a rate of 10 °C/min.
The acid site types of the samples were determined using infrared
spectroscopy of pyridine adsorption (Py-IR) on a Nicolet 6700
spectrometer from the United States. The catalyst was dried at 120 °C
for 12 h and then cooled to room temperature before the introduction
of pyridine. Pyridine vapor was allowed into the chamber for 24 h to
achieve a saturation adsorption of pyridine. Subsequently, the samples
were rinsed using a He stream for 2 h at 150 °C.
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Energy Fuels 2024, 38, 4256−4272
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Figure 1. N2 adsorption−desorption isotherms of all catalysts.

2.4. Depolymerization Experiments of Lignin. The LCD weight of the monomer

monomer yield(mg/g lignin) = × 100
experiment process is described in Scheme 1c. Initially, a mix of 1.0 g weight of lignin
of lignin, 0.2 g of the catalyst, and 30 mL of ethanol was stirred using (3)
a magnetic stirrer in a 100 mL stainless-steel reactor (Shanghai 2.5. Lignin Model Compound Experiments. The process of
Yanzheng Experimental Instrument Co., Ltd., Shanghai, China). The catalytic conversion of PP as the lignin model compound was
reactor was then purged with N2 to remove air and filled with 0.2 MPa consistent with lignin depolymerization (reaction conditions: 0.1 g of
N2. Subsequently, the reactor was heated to the target temperature the lignin model compound PP, 0.02 g of the catalyst, and 30 mL of
and stirred continuously at 450 rpm for the established time. After ethanol). The conversion and monomer selectivity of PP were
completing the reaction, the reactor was immediately placed in ice calculated by the following equations:
water and cooled to room temperature. The liquid and solid phases conversion of PP(conv. %)
were separated by vacuum filtration to obtain the respective products. mole of the residual substrate
The remaining ethanol in the liquid product was eliminated by using a = (1 ) × 100%
mole of the initial substrate (4)
rotary evaporator at 40 °C. The liquid product was obtained, while
the solid product (char and catalyst) was washed with acetone and mole of the product
monomer selectivity(%) = × 100%
dried at 105 °C for 12 h. The yields of liquid, solid, and monomer mole of the reacted substrate
products were calculated using the following formula: (5)
On the premise of the Arrhenius equation, the reaction rate and the
yield of the liquid product (%) apparent activation energy (Ea) of the conversion reaction of 2-
weight of the liquid product phenoxy-1-phenylethanol (PP) were calculated using the following
= × 100% formulas, assuming it to be a pseudo-first-order reaction:
weight of lignin (1)
ln(1 conv. ) = kt (6)

yield of the solid product (%) Ea

ln k = ln A
yield of the solid product weight of the catalyst RT (7)
= × 100%
weight of lignin where conv. represents the conversion of the model compound, k is
(2) the rate constant, R signifies the constant of molar gas (8.314 J·mol−1·

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K−1), T denotes the reaction temperature, and A represents the pre-
exponential factor.
2.6. Analysis of the Depolymerization Product. The
elemental contents of carbon, hydrogen, oxygen, nitrogen, and sulfur
in both lignin and liquid products were determined by employing a
Vario EL III elemental analyzer (Germany). The higher heating value
(HHV) was obtained according to Dulong’s formula: HHV (MJ/kg)
= 0.3491 × C + 1.1783 × H + 0.1005 × S − 0.1034 × O − 0.0151 ×
N − 0.0211 × ash.10
The gas chromatography−mass spectrometry (GC-MS) technique
was utilized to analyze both the liquid and model conversion
products. A Thermo Scientific ISQ 7000 MS detector from the USA
and a TG-5SILMS capillary column (30 m × 0.25 mm × 0.25 μm)
were used. To begin with, the oven was kept at a consistent
temperature of 50 °C for 3 min followed by a gradual increase to 280
°C at 10 °C min−1. The end product, the yield of the monomer, was
determined using a known amount of acetophenone as an internal
standard.
A Bruker AVANCE NEO 600 MHz spectrometer (Germany) was
used to record the 2D-HSQC NMR spectra of both lignin and liquid
products. Dimethyl sulfoxide-d6 (DMSO-d6) was utilized as a sample
solvent, while the remaining DMSO solvent peak (δC/δH 39.5/2.50)
was employed as an internal reference.
dispersed on the SEP surface, resulting in creating abundant
regenerated pores. Meanwhile, for Zr/SEP, the addition of Zr
clearly reduced the SBET and Vpore to 4.83 m2/g and 0.01 cm3/
g, respectively, in comparison with SEP. This might because
the impregnation process of Zr4+ precursors led to the entrance
of Zr4+ into slit-pores of SEP. As compared with Co/SEP, it
was observed that the SBET and Vpore of Co−Zr/SEP catalysts
were obviously decreased with the decrease of Co/Zr mass
ratios. Among Co−Zr/SEP catalysts, 3Co1Zr/SEP had the
highest SBET (198.11 m2/g) and Vpore (0.716 cm3/g). This
further confirmed the above analyses about the effect of Co
and Zr species on textural properties. Therefore, it was
reasonable to conclude that in Co−Zr/SEP catalysts, Co
species mainly led to form irregular mesopores on the SEP
surface, while Zr species uniformly distributed in the
mesopores.
The phase and crystal structures of all samples were analyzed
using XRD, and the outcomes are depicted in Figure 2. For

3. RESULTS AND DISCUSSION

3.1. Characterization Analysis of As-Prepared Cata-
lysts. The as-prepared catalysts' textural properties were
discussed by N2 adsorption−desorption, and the results are
presented in Figure 1 and Figure S1. It was found that SEP and
Zr/SEP exhibited typical IV adsorption−desorption isotherms
with H3 hysteresis loops in accordance with the IUPAC
classification, indicating that they had slit-pores formed by the
stacking of sheetlike nanoparticles, which are the typical
morphological features of SEP.35 However, the as-prepared
catalysts containing Co species presented typical IV
adsorption−desorption isotherms with H4 hysteresis loops,
and these loops were shrunk with the increase of the Zr
content, indicating that their pores were irregularly meso-
porous predominantly derived from the cobalt oxides. In
addition, the appearance of “tails” at P/P0 = 0.01 in all as- Figure 2. XRD patterns of all catalysts.
prepared Co-based catalysts indicated the existence of a
minimal amount of micropores and irregular mesopores.51 For SEP, the characteristic diffraction peaks at 2θ = 8.99, 14.09,
further analysis, the as-prepared catalysts' specific surface area 17.87, 24.5, 26.7, 30.06, 42.6, 19.85, 31.88, 34.78, and 37.35°
(SBET) and average pore volume/size (Vpore/Dpore) are listed in correspond to SEP.50 Upon incorporating Co and Zr, it was
Table 1. For Co/SEP, its SBET and Vpore were dramatically apparent that the intensities of the peaks of SEP were
significantly reduced due to the interaction between the Co/Zr
Table 1. Textural Parameters for All Catalysts species and SEP to cover the surface of SEP. Furthermore, for
SBET Vpore Dpore Co Zr Co/SEP, the peaks at 2θ = 31.2, 36.8, and 44.8° are related to
samples (m2/g) (cm3/g) (nm) (wt %) (wt %) Si/Al the (220), (311), and (400) crystal planes of Co3O4, and the
SEP 19.69 0.066 13.02 1.41 peak at 2θ = 37.8° corresponds to the characteristic diffraction
Co/SEP 244.43 0.911 13.23 19.11 1.32 peak of Co(OH)2, which was attributed to the incomplete
3Co1Zr/ 198.11 0.716 13.57 14.29 4.81 1.39 conversion of Co(OH)2 to Co3O4 during the calcination
SEP process. For Zr/SEP, characteristic diffraction peaks of ZrO2
1Co1Zr/ 190.50 0.522 10.48 8.95 9.65 1.35 with a typical mixture of monoclinic and tetragonal phases
SEP
were detected at 2θ = 28.2, 29.9, 31.6, and 50.2°. In addition,
1Co3Zr/ 99.15 0.112 4.52 4.74 13.86 1.39
SEP in Co−Zr/SEP catalysts, only the characteristic peaks of
Zr/SEP 4.83 0.010 10.55 19.13 1.44 Co3O4 were observed without finding the peaks of Co(OH)2
and ZrO2. It was implied that the homogeneous dispersion of
Zr into the mesopores and the Zr additive promoted the
increased to 244.43 m2/g and 0.911 cm3/g, respectively, as conversion of Co(OH)2 into Co3O4 mainly via forming the
compared with those of SEP. It might be attributed to that the interaction between Zr and Co components.
Co2+ precursors that interacted with OH− species during the All samples' metal−oxygen bonds and surface groups were
precipitation to form Co(OH)2 species, and then, they were further investigated by FTIR analysis (Figure S2). The
converted to cobalt oxides during the calcination process. The vibrational bands at 3700−3300 cm−1 were derived from the
formed cobalt oxides interacted with the SEP framework and vibrations of the OH− groups, the band at 1644 cm−1 was
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associated with SEP structured water. The vibrational bands at
1010, 470, and 541 cm−1 were the symmetrical and
asymmetrical vibrations of Si−O bonds of silica in SEP
tetrahedral sheets.35 When the Co and Zr species were
introduced, the vibrational bands of the SEP at 1010 and 470
cm−1 were blueshifted, which indicated that there were
interactions between the Co and Zr species and the surface
of the SEP. For Co−Zr/SEP catalysts, the bands at 571 cm−1
correspond to the vibrations of Co3+ atoms at the octahedral
sites of Co3O4, and the bands at 664 cm−1 were ascribed to the
vibrations of Co2+ atoms at the tetrahedral positions of
Co3O4.47 Meanwhile, these bands were not observed in Co/
SEP, which is probably attributed to the fact that the Co(OH)2
species as detected by XRD affected the vibrations of Co3+ and
Co2+ atoms in Co3O4 species. In addition, except for Zr/SEP,
there was no appearance of bands at 526 and 746 cm−1
attributed to the signals of Zr−O bonds of ZrO2 that appeared
in the other Zr-containing catalysts. It was suggested that the
Zr species did not exist in the form of ZrO2 in Co−Zr/SEP
catalysts, and the reason for this situation might be attributed
to the interaction of ZrO2 with Co species.
To further investigate the effect of the addition of Co and Zr
on the skeletal structure of SEP, Raman characterization was
performed on all catalysts, and the obtained spectra are
displayed in Figure 3. It can be found that the intensities of
Figure 3. Raman patterns of all catalysts.
SEP Raman peaks at 252, 451, and 698 cm−1 decreased or
disappeared with the incorporation of Co and Zr. This
demonstrated that the formation of the interaction of Co and
Zr species with SEP weakens the Raman signal of SEP. For
Co/SEP, the Raman bands at 482, 522, 616, and 686 cm−1
correspond to the E2g, F22g, F2g, and A1g phonon modes of the
Co3O4 phase, respectively.41 In addition, the peak at around
595 cm−1 corresponds to the mixture of Co(OH)2 and Co3O4.
The Co(OH)2 species in Co/SEP was not fully converted to
Co3O4 generally attributed to Co(OH)2 present in the outer
layer of the catalyst, which was easily determined by the
Raman laser. For Zr/SEP, the Raman peak at 263 cm−1 is
specific to the tetragonal phase of ZrO2, and the Raman peaks
at 480 and 634 cm−1 were attributed to the ZrO2 monoclinic
phase. In Co−Zr/SEP, the characteristic bands attributed to
the phonon modes of the Co3O4 were all detected, while the
addition of Zr species resulted in the blueshift of the Raman
pubs.acs.org/EF Article
characteristic peaks of Co3O4 at 686 cm−1 (A1g) ascribed to the
octahedral sites (CoO6). This demonstrated that the original
octahedral coordination environment in Co3O4 was altered
and consequently increased the number of defect sites.
Notably, since no diffraction peak of Co(OH)2 was observed
in 3Co1Zr/SEP by XRD analysis, the Raman peak appearing at
595 cm−1 might be the CoOx oxides produced by the
transformation of Co(OH)2 to Co3O4 (under the calcination
process as described in the section Catalyst Preparation). This
had also been reported by Gao et al.52
The Co/SEP and 3Co1Zr/SEP were further selected for
HRTEM coupled with elemental mapping to study the
influence of Zr species on the microscopic morphology and
crystal composition, and the obtained results are displayed in
Figures 4 and 5. In accordance with the results of elemental
mapping in Figure 4a, the Co, Al, Si, and O elements uniformly
distributed in Co/SEP. For 3Co1Zr/SEP as shown in Figure
5a, the above four elements were uniformly distributed, but the
Zr element was partially overlapped. This was mainly caused
by the Zr predominantly distributed into the irregular
mesopores formed by the deposition of Co species on the
SEP surface. In the HRTEM images of Co/SEP displayed in
Figure 4b, according to our previous report,47 the fibrillar
phyllosilicate species were clearly observed, which was due to
the interaction of Co species with Si species in SEP to form
Co-phyllosilicate structures. Since the formation of Co-
phyllosilicate changed the original structure of SEP, the Al
atoms in SEP were also exposed and distributed near the Co-
phyllosilicate. Therefore, the characteristic lattice spacings of
0.304 and 0.447 nm corresponding to the Al2O3 (022) and
(002) crystal faces were observed as shown in Figure 4c. In
addition, the Co3O4 with the given lattice spacing of 0.286 nm
corresponding to the (220) crystal plane in the neighborhood
of the Co-phyllosilicate in Figure 4d was observed. In the
HRTEM images of 3Co1Zr/SEP, Co-phyllosilicate fibers and
the characteristic crystal planes of Al2O3 (122), (022), and
(002) were also observed (as presented in Figure 5b,c). In
addition, the lattice spacings of 0.202, 0.244, and 0.286 nm
attributed to the characteristic crystal planes of Co3O4 (220),
(311), and (400), respectively, were observed in Figure 5d,e,
which are in line with the results of XRD. It was suggested that
the addition of Zr generated the interaction between Zr and
Co species, which promoted the exposure of Co3O4 crystal
planes and provided more reactive sites for LCD. In addition
to this, the lattice spacing of 0.219 nm corresponding to the
(201) crystal plane of ZrO2 was also detected.
H2-TPR measurements were performed to further study the
interaction of Co with Zr and SEP. As shown in Figure S3, the
reduction profile of Co/SEP exhibited the broad peak at 320
°C, which corresponded to the reduction of Co(OH)2 and Co
oxides, and the peak at about 730 °C was attributed to the
reduction of Co-phyllosilicate.47,55 According to the re-
ports,44,56 there was almost no occurrence of the ZrO2
reduction peak in the H2-TPR profile. Consequently, the
weak reduction peak at 600 °C in the Zr/SEP TPR profile
mainly corresponded to the reduction of ZrO2−x species that
were produced by the interaction between SEP and the Zr
species but not the ZrO2 reduction. For Co−Zr/SEP catalysts,
the peaks in the 250−450 °C region corresponded to the
reduction of Co3O4 to Co0 (Co3O4 → CoO → Co0), and the
peaks in the high-temperature region (>600 °C) correspond to
the reduction of Co-phyllosilicate. Obviously, the reduction
temperature of Co-phyllosilicate was significantly decreased
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Figure 4. Corresponding element mapping (a) and HRTEM images (b−d) of Co/SEP.
Figure 5. Corresponding element mapping (a) and HRTEM images (b−e) of 3Co1Zr/SEP.
with the addition of Zr, which suggested that the interaction
between Co species and Zr species decreased the Co-
phyllosilicate species. This further demonstrated that the
addition of Zr species resulted in more conversion of Co
species to Co3O4 species rather than the formation of Co-
phyllosilicate, which was consistent with the XRD and Raman
results.
To explore the surface chemical states of the different
elements and the interactions among the various components,
XPS characterization was conducted for all catalysts, and the
obtained XPS spectra of Co 2p, Zr 3d, and O 1s are shown in
Figure 6. It was seen that the Co 2p XPS spectra were split into
two major peaks at about 781.4 and 797.1 eV accompanied
with satellite (sat.) peaks at about 786.5 and 803.4 eV, which
are attributed to the Co 2p1/2 and Co 2p3/2 originated from the
split of spin orbits of the Co 2p orbital in Figure 6a.
Furthermore, following deconvolution treatment, the Co 2p
XPS spectrum could be divided into three doublets. The
coupled peaks at 779.9 and 795.2 eV were correlated to Co3+
of Co3O4 species, and the binary peaks at 781.2 and 797.5 eV
were attributed to Co2+ of Co3O4 species, while the conjugated
peaks at 782.5 and 798.5 eV corresponded to a mixture of
Co(OH)2 and CoOx species (2 < x < 3).41,52 It was found that
Co(OH)2 and CoOx in Co/SEP were the major existential
states of the Co species. Compared with Co/SEP, the peak
area of the mixture of Co(OH)2 and CoOx species gradually
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reduced with the decrease of Co/Zr ratios. Based on the results
of XRD and Raman analysis, this might be attributed to the
combined action of the Zr additive promoting the trans-
formation of Co(OH)2 into CoOx species and the decrease of
the Co content in the catalyst. Additionally, in Co−Zr/SEP
catalysts, the relative contents of Co3+ and Co2+ of Co3O4
species increased with the decrease of the Co/Zr ratio,
suggesting that the inclusion of Zr species facilitated the
creation of Co3O4, which was consistent with the results of
Raman analysis and H2-TPR.
Figure 6b exhibits the Zr 3d XPS spectra for all catalysts. In
the control group of Zr/SEP, the peaks at about 184.2 and
181.9 eV were related to Zr3+ species according to the reports
in refs 44 and 56. Generally, Zr(NO3)4·5H2O as the precursor
salt of the Zr additive could be completely converted to ZrO2
under 4 h of calcination at 500 °C in an air atmosphere, which
was the necessary process for catalyst preparation in this paper.
Therefore, the appearance of Zr3+ species in Zr/SEP was
attributed to the interaction of Zr species with the SEP
framework, which confirmed the existence of electron transfer
between the SEP framework and Zr. For 3Co1Zr/SEP, the two
main peaks at about 185.0 and 182.8 eV were related to Zr
3d3/2 and Zr 3d5/2 orbits, demonstrating the existence of Zr4+
species according to the reports in refs 44 and 56.
Furthermore, the peaks of Zr 3d3/2 and Zr 3d5/2 in other
catalysts shifted straightly to lower binding energies with the
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Figure 6. XPS of (a) Co 2p, (b) Zr 3d, and (c) O 1s energy regions of catalysts. (d) EPR spectra of catalysts.
decrease of the Co/Zr ratio, which suggested that valence state
of Zr decreased gradually with the Zr addition. The correlation
between the change in the valence state of Zr species and the
Co/Zr ratio can be clarified here. It should be pointed out that
in Co−Zr/SEP catalysts, the Co species were first supported
on SEP then introduced with Zr species during catalyst
preparation. In 3Co1Zr/SEP, the sufficient Co species first
contacted and covered the SEP surface and resulted in the Zr
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species not approaching the SEP surface; therefore, only Zr4+
species were found. With the reduction of the Co content, the
SEP surface was not completely covered, and then, some Zr
species interacted with SEP leading to the Zr 3d XPS peak
moving into lower binding energies such as in 1Co1Zr/SEP
and 1Co3Zr/SEP.
Figure 6c shows the XPS spectra of O 1s of all samples. After
undergoing deconvolution treatment, the XPS spectra of O 1s
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Figure 7. (a) NH3-TPD profile and (b) Py-IR spectra of SEP, Co/SEP, and 3Co1Zr/SEP.
could be resolved into four distinct peaks: 530.3 (lattice
oxygen), 531.1 (Vo, oxygen vacancy), 531.8 (surface hydroxyl
oxygen), and 532.4 eV (adhering water). The formation of
adhering water on the catalyst surface was basically attributed
to its SBET, and the amount of adsorbed water was positively
correlated with the SBET of the catalyst. Therefore, the adhering
water content of various catalysts as presented in Figure 6c
exhibited a positive correlation with their specific surface areas
(listed in Table 1). The peak at 531.8 eV represented the
surface hydroxyl oxygen of the catalyst, and it is known that the
surface hydroxyl groups are correlated with the amount of
BAS.33,35 In addition, Figure 6c displays the surface relative
proportion of various O species, it was found that the VO
content of 3Co1Zr/SEP was increased as compared with Co/
SEP, which is generally attributed to the conversion of
Co(OH)2 to CoOx. With the increase of the Zr content, the Zr
species promoted the conversion of Co species to Co3O4, and
thus, the VO content of 1Co1Zr/SEP further decreased. It was
noteworthy that the VO content of 1Co3Zr/SEP was
significantly increased, but its CoOx content was very low
(as confirmed by Co 2p XPS). This suggested that the
increased VO did not originate from the CoOx species but from
the Zr species.58
In addition, electron paramagnetic resonance (EPR) was
utilized to validate the influence of Zr addition on VO
concentration. As a result of the generation of VO, the cations
became undercoordinated, leading to a decrease in the electron
density of the system. This caused the electrons to become
localized in the center of the cations, which then captured
them and acquired magnetism;51 the EPR signal could
represent the concentration of VO. The EPR signal with g =
2.003 corresponded to VO as demonstrated in Figure 6d. The
3Co1Zr/SEP signal intensity was higher than that of Co/SEP,
and the signal intensity of 1Co1Zr/SEP was less than that of
3Co1Zr/SEP, which confirmed the conclusion that the VO was
related to the CoOx content. Furthermore, 1Co3Zr/SEP had
the highest signal intensity, which further supported the above
XPS discussion result.
NH3-TPD was employed to study the amount of surface
acid sites of as-prepared catalysts, and the obtained profiles are
displayed in Figure 7a. The NH3 desorption peaks could be
4264
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categorized into three temperature regions, which correspond
to weak, medium, and strong acid sites. Moreover, the HN3-
TPD profiles demonstrated that the medium acidic sites of the
SEP surface were predominant, and the total acidity was 0.31
mmol NH3/g. For Co/SEP, the surface acid sites increased
significantly in terms of weak acid sites and medium acid sites
in comparison with SEP. Generally, the rise in weak acidic sites
was attributed to the introduction of Co active species that
promoted the weak absorption of NH3 molecules.55 Mean-
while, the augment of medium acid sites was ascribed to the
increase of −OH groups originated from Co(OH)2 that
resulted in the medium absorption of NH3 molecules on the
surface of the catalyst.39,41 With the addition of Zr into Co/
SEP, it was observed that the distribution of weak and medium
acid sites indicated almost no changes in 3Co1Zr/SEP
compared with Co/SEP. However, the total acidity decreased
to 0.47 mmol NH3/g for 3Co1Zr/SEP from 0.62 mmol NH3/g
for Co/SEP. This was mainly because the Zr additive
promoted the conversion of Co(OH)2 species to CoOx as
confirmed by XRD. Another interesting finding was that the
strong acid sites were detected in 3Co1Zr/SEP, which was
mainly assigned to absorption of NH3 molecules on the
coordination-unsaturated Zrδ+ or electron-deficient metal
oxides (CoOx) based on the report of Ranaware et al.59
Py-IR as presented in Figure 7b recognized the Brønsted
(BAS) and Lewis acid sites (LAS) and determined their
relative amounts summarized in Table 2. The vibrational bands
at 1447−1450 and 1599−1610 cm−1 were attributed to the
LAS, the vibrational bands at 1548 and 1650 cm−1 were
attributed to the BAS, and the band at 1490 cm−1 was
Table 2. Acid Site Types and Density of Catalysts
Determined by NH3-TPD and Py-IR
acid sites
(μmol Py/g)
catalyst total acidity (mmol NH3/g) Lewis Brønsted L/B
SEP 0.31 66.5 2.5 26.6
Co/SEP 0.62 26.4 1.9 13.9
3Co1Zr/SEP 0.47 216.2 4.3 50.3
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Figure 8. Liquid product and solid product yield over different catalysts (a), selectivity of different monomers over different LP (b), and monomer
yield over different LP (c). Reaction conditions: 1 g of lignin, 0.2 g of the catalyst, 30 mL of ethanol, 0.2 MPa N2 initial pressure, 290 °C, 4 h, 450
rpm.
attributed to the mixture of BAS and LAS.41,50 For SEP, the
peaks at 1447−1450 and 1599−1610 cm−1 were significantly
stronger than those at 1548 and 1650 cm−1, which indicated
that the amount of LAS on the SEP surface was obviously
higher than that of BAS. Compared to SEP, the L/B ratio of
Co/SEP was decreased due to the presence of partially
unconverted Co(OH)2 on the surface of Co/SEP. In addition,
the amount of LAS and BAS was reduced for Co/SEP
compared to SEP. This was due to the low transmittance of
fuscous Co/SEP during testing, which resulted in much lower
amounts of LAS and BAS than the actual amounts.34 The
elevated ratio of L/B for 3Co1Zr/SEP compared with Co/SEP
was attributed to the incorporation of Zr, which promoted the
conversion of Co(OH)2 and reduced the amount of −OH on
the surface.
3.2. LCD Experiments of Co−Zr/SEP Catalysts.
3.2.1. Catalyst Performance and Liquid Product Character-
ization. In order to investigate the LCD performance of as-
prepared catalysts, the reaction was performed for 4 h at 290
°C, and the yields of liquid and solid products are displayed in
Figure 8. With SEP as a catalyst, the yield of liquid products
was only 27.44%, but the yielded solid product reached to
71.76%. After the individual addition of Co and Zr, the yields
of liquid products over Co/SEP and Zr/SEP were increased to
46.71 and 29.62%, respectively. Meanwhile, the corresponding
yields of solid products were slightly reduced to 52.09 and
66.28%, respectively. This is mainly attributed to the
introduction of the Co and Zr-containing species enabling
the activation of ethanol to produce more in situ hydrogens,
which enabled the hydrogenation of reactive intermediates and
reduced the production of char. It had been confirmed that
Co-based catalysts could promote the performance of aqueous-
phase reforming of ethanol hydrogen production.61 For Co−
Zr/SEP, it was revealed that only 3Co1Zr/SEP showed the
best catalytic performance, in which the yield of liquid
products reached to 60.11%, while the solid product yield
decreased to 38.49%. It was mainly attributed to the higher
SBET, the highly dispersed metal sites, and abundant acidic sites
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over 3Co1Zr/SEP promoting the cleavage of the lignin C−C
and C−O bonds and their derived intermediates. Additionally,
the recyclability of 3Co1Zr/SEP was investigated, and the
results are shown in Figure S4. The liquid yield decreased after
each cycle, and the liquid product yield decreased to 41.59%
after five cycles, indicating that the active sites of the catalyst
were changed. Figure S4b,c indicates that the species of the
catalysts were changed, in which the CoOx active phase almost
disappeared and transformed to Co3O4. In addition, the
decrease in the amount of acid from the spent catalysts was
also one of the reasons for the deactivation of the catalysts.
The GC-MS analysis coupled with an internal standard
method was conducted for further evaluating the composition
of the monomer in the liquid products. For convenience, the
liquid products (LP) that were obtained by using SEP, Co/
SEP, 3Co1Zr/SEP, 1Co1Zr/SEP, 1Co3Zr/SEP, and Zr/SEP
were named as LP-1−6, respectively. The obtained GC-MS
spectra are shown in Figure S5, and the specific information on
monomers is listed in Table S1. As a whole, the monomers in
these liquid products reached to 33, and these compounds
could be divided into three categories, namely, guaiacols (red),
alkylphenols (orange), and others (black). Furthermore, the
selectivities and yields of the three categories are exhibited in
Figure 8b,c. The guaiacol selectivity in LP-1 reached to 88.61%
along with a yield of 243.1 mg/g lignin. Our previous work had
demonstrated that the acidic sites exposed on the SEP surface
could promote the lignin C−C and C−O bond break-
age.33−35,50 It was found that the selectivity of guaiacols in
the LP-2 and LP-6 slightly decreased to 78.33 and 89.32%,
respectively. Meanwhile, the selectivity of alkylphenols in LP-2
increased to 15.05%, while that in LP-6 decreased to 8.19%.
These results demonstrated that Co species exhibited a more
significant promotion effect on LCD in comparison with Zr
additives. It was observed that the selectivity of guaiacols in
LP-3 decreased to 74.06%, but the selectivity of alkylphenols
obviously increased to 18.27 as compared with LP-2 and LP-6.
Meanwhile, as compared with LP-3, the selectivity of guaiacols
of LP-4 decreased to 70.29%, while the selectivity of
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Table 3. Elemental Composition of Lignin and the Liquid Product
elemental contents (wt %)
samples C H O N
lignin 57.84 4.63 22.98 0.89
LP-2 71.29 7.72 18.87 0.60
LP-3 71.94 8.01 17.96 0.62
Figure 9. FTIR patterns (a) and 1H NMR spectra (b) of lignin and LP-3.
alkylphenols increased to 22.85%. However, it was noteworthy
that the selectivity of guaiacols of LP-5 increased to 85.31%
while that of alkylphenols decreased to 11.23% with the further
increase of the Zr content. These results confirmed that the
addition of Zr could promote the alkylation reaction during
LCD, but the superabundant Zr content did not facilitate the
alkylation reaction.
It should be pointed out that the yields of guaiacols and
alkylphenols in LP-3 all reached to the highest values, which
were 445.2 and 109.8 mg/g lignin, respectively, as presented in
Figure 8c. This suggested that there was a synergistic effect
between Co and Zr additives. Based on above discussion, it
could be concluded that Co species could promote the
cleavage of lignin C−C and C−O bonds and had facilitating
effects on in situ hydrogen production. In addition, the
addition of Zr resulted in more LAS and VO for the catalyst, in
which LAS could promote the cleavage of C−C and C−O
bonds, and VO could adsorb and stabilize the reactive
intermediates and inhibit the condensation reaction. In
summary, the synergistic effect between Co and Zr promoted
the generation of more active intermediates, which led to the
increase of subsequent hydrogenation and alkylation reactions,
resulting in the optimal LCD performance for 3Co1Zr/SEP.
VO was also one of the reasons for the highest yield of
guaiacols (445.2 mg/g lignin), where VO adsorbed and
stabilized the reactive intermediates in the LCD process,
inhibited the occurrence of polycondensation reactions, and
facilitated further hydrogenation or alkylation reactions of the
intermediates.40,41,51 When 1Co3Zr/SEP was used as the
catalyst, which was almost the same as the product
composition of LP-6, the main reason for the decrease in the
alkylation reaction at this time was that Zr species dominated
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S ash H/C O/C HHV (MJ/kg)
2.28 2.12 0.08 0.40 23.44
0.26 0.17 0.11 0.26 32.05
0.22 0.14 0.11 0.25 32.71
the catalyst, and Zr species did not promote LCD significantly
and inhibited the promotion of Co species for LCD.
In addition, elemental analysis of the lignin and the liquid
product under the three reaction conditions was performed to
determine the elemental content of the samples. The higher
heating value (HHV) was calculated and is summarized in
Table 3. Compared to lignin, the value of H/C of the LP
samples increased, while the value of O/C decreased, which
indicated that effective depolymerization of lignin was achieved
in the presence of the catalyst. Compared to LP-2, LP-3
showed a lower O content and higher C and H contents, which
was related to the increased products of alkylation. Compared
to lignin, the HHV of LP-3 obtained by 3Co1Zr/SEP
increased significantly to 32.71 from 23.44 MJ/kg of lignin.
To further investigate the change in structural information
from lignin to the liquid product, FTIR, 1H NMR, and 2D-
HSQC NMR analyses were conducted on lignin and the LP-3.
Figure 9a illustrates the FTIR spectra of lignin and LP-3, and
the specific characteristic vibrations are given in Table S2. The
bands at 2960, 2920, and 2875 cm−1 correspond to the
stretching vibrations of methyl, methylene, and methyne
groups, respectively, and the band at 1460 cm−1 was attributed
to the bending vibrations of the methylene functional groups.33
Furthermore, the band at 1510 cm−1 corresponds to the
skeleton vibration of the aromatic ring.33,60 Meanwhile, the
bands at 1120 cm−1 are attributed to the C−O bond stretching
vibrations in the syringyl unit.33 The bands at 1085 and 1030
cm−1 are correlated to the primary and secondary alcohol
groups stretching vibrations, respectively.33,60 Compared to
lignin, LP-3 showed stronger vibrational bands at 2960, 2920,
2875, and 1460 cm−1. The weakened signals in the LP-3 band
at 1510 cm−1 might be due to the breakage of the connecting
bond of the structural unit of the lignin, and the products were
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Figure 10. 2D-HSQC NMR spectra of lignin before the reaction (a,c) and LP-3 after the reaction (b,d).
more concentrated. The disappearance of the band at 1120
cm−1 in the lignin further suggested the breakage of the
connecting bond of the lignin structural unit. Furthermore, the
enhancement of the band signals located at 1085 and 1030
cm−1 demonstrated an increase of primary and secondary
alcohol groups in LP-3.
Similarly, the 1H NMR spectra of lignin and LP-3 are shown
in Figure 9b and divided into three regions: the methyl and
methylene region, methoxy region, and aromatic region.51 The
enhanced signal in the methyl and methylene regions of LP-3,
the disappearance of part of the signal in the methoxy and
aromatic region of lignin, and the more concentrated signal in
the methoxy and aromatic region of LP-3 were observed. The
results discussed above all indicated that the C−C and C−O
bonds used to connect the lignin basic units were sufficiently
disrupted during the LCD process.
2D-HSQC NMR was further employed to investigate the
structural changes of lignin and LP-3, and the obtained results
are exhibited in Figure 10 and Figure S7. According to a
previous report,51 the regions of [δC/δH 50−90/2.5−5.5] and
pubs.acs.org/EF Article
[δC/δH 90−135/6.0−8.0] correspond to the aliphatic side-
chain region and the aromatic region, respectively. For lignin,
the signals of Aα (δC/δH 73.2/4.76, orange), Aβ (δC/δH 84.2/
4.30, orange), and Aγ (δC/δH 59.8/3.80, orange) correspond-
ing to the β-O-4 bonds of lignin could be seen. Additionally,
the observed signals of Bγ (brown), Cα, Cβ (pink), and Fγ
(green) were attributed to C−O bonds in the side-chain region
of lignin. For LP-3, the signals of Aα, Aβ, Aγ above-mentioned
disappeared, which indicated that the β-O-4 and side-chain C−
O bonds were broken. In addition, the increased signal in the
Csp3-H region [δC/δH 10−50/0−2.5] for LP-3 as presented in
Figure S7 was attributed to the hydrogenation that allowed the
substitution of oxygen by hydrogen to form an alkylated
product when the C−O bond was broken, in line with the
results of GC-MS and FTIR. The liquid product had more
concentrated signals in the aromatic ring region compared to
lignin, suggesting that a portion of the aromatic ring structure
had disappeared, and the product was more concentrated as
the guaiacyl unit structure. There is also a disappearance of
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Figure 11. Effect of reaction temperature (a) and reaction time (b) over the 3Co1Zr/SEP catalyst.

other signals in the region, indicating the excellent ability of the

prepared 3Co1Zr/SEP to break C−O bonds.
3.2.2. Effect of Reaction Time and Temperature on LCD.
Commonly, LCD is strongly influenced by the temperature
and the time of the reaction. The influence of reaction
temperatures on LCD over 3Co1Zr/SEP for 4 h was
investigated, and the results are presented in Figure 11a. The
temperature was raised from 230 to 290 °C. This brought
about the increase in the production of LP from 28.34 to
60.11%, while the yield of solid products dropped from 70.66
to 38.49%. It was suggested that the elevated temperature
facilitated the broken chemical bonds of the lignin structure
and the production of activated hydrogen in the ethanol
system, while the active intermediates generated from lignin
degradation further reacted with the activated hydrogen to
obtain the small-molecule monomer products. When the
temperature was raised to 310 °C, the LP yield decreased to
52.68% and the solid product yield increased to 42.12%. This
is generally attributed to the excessive high temperature that
accelerated the polycondensation reaction of the intermediate
fragments. In addition, lignin-derived macromolecular frag-
ments were also carbonized at excessive temperatures resulting
in the increase of the solid product.
The influence of reaction time on LCD over 3Co1Zr/SEP at
290 °C was investigated, and the outcomes are presented in
Figure 11b. It was found that the yields of the LP exhibited a
clearly increased tendency with the reaction run from 1 to 12
h, while the solid product yield presented the gradual
reduction. The yield of the LP increased to 78.83%, and the
solid product decreased to 20.23% after 12 h of reaction. In
addition, the GC-MS results of the LP obtained after different
reaction times are presented in Figure S9. This confirmed that
the alkylation products significantly increased with reaction
times. These results demonstrated that the elongation of
reaction time could facilitate the lignin depolymerization
reaction, while the guaiacols could continue to undergo
alkylation to produce alkylphenols.
3.3. The Bond-Breaking Mechanism of β-O-4 and
Kinetic Analysis. To investigate the bond-breaking ability of
3Co1Zr/SEP on lignin, the model compound PP (2-phenoxy-
1-phenylethanol), which has the typical linkage bond (β-O-4)
of lignin, was chosen for depolymerization experiments. As
shown in Figure 12, the conversion of PP reached 99.01%
4268
Figure 12. PP conversion and product selectivity on the 3Co1Zr/SEP
catalyst as a function of time. Reaction conditions: 0.1 g of PP, 0.02 g
of the catalyst, 30 mL of ethanol, 50 mg of n-dodecane as an internal
standard, 0.2 MPa N2 initial pressure, 240 °C, 450 rpm.
when the reaction lasted for 150 min, and the monomers that
converted from PP mainly contained phenol, phenethyl
alcohol, and phenylacetaldehyde according to the results of
GC-MS as presented in Figure S10. The other byproduct
benzaldehyde was generated by breakage of the Cα−Cβ bond
or a condensation reaction. As the reaction time increased, the
monomer product of phenylacetaldehyde was further hydro-
genated to form phenethyl alcohol; consequently, the
selectivity of phenylacetaldehyde gradually reduced with a
concomitant increase of phenethyl alcohol selectivity. There-
fore, according to the experimental outcomes and previous
studies, the β-O-4 linkage in PP was broken in the following
steps: generally, the H+ derived from ethanol activation over
Co metallic sites would attack the Cα−OH to promote the
dehydration reaction to remove the hydroxyl groups of PP;
then, the reactive Cα* species would rearrange in the electron-
deficient environment to generate the (2-phenoxyvinyl)-
benzene intermediate, which instantaneously hydrolyzed into
phenylacetaldehyde and phenol; then, phenylacetaldehyde
underwent the hydrogenation reaction to form phenethyl
alcohol.62 Subsequently, the other pathway involved the
https://doi.org/10.1021/acs.energyfuels.3c04637
Energy Fuels 2024, 38, 4256−4272
Energy & Fuels
Figure 13. (a) SEP and (b) 3Co1Zr/SEP catalyst for PP conversion as a function of reaction temperature and reaction time. (c) Arrhenius plots for
SEP and the 3Co1Zr/SEP catalyst for PP conversion.
Scheme 2. Possible Reaction Pathway for LCD
breaking of the Cα−Cβ under the influence of LAS and Co
metal sites to produce benzaldehyde and anisole, and the
anisole was hydrogenated to crack the C−O in methoxy to
produce phenol.
Furthermore, Figure 13 displays the impact of catalysts on
the thermodynamic characteristics associated with the cleavage
of the β-O-4 bond in PP. Figure 13a,b shows the well first-
order linear relationship between the reaction time and ln(1 −
conv.) of PP over SEP and 3Co1Zr/SEP. It was observed that
pubs.acs.org/EF Article
the slopes varied with the increase of the temperature,
indicating that there was a close relationship between the
reaction rate and the temperature. Subsequently, the Arrhenius
formula was used to calculate the apparent activation energies
(Ea) for PP conversions catalyzed by the SEP and 3Co1Zr/
SEP. The Ea for PP conversion over SEP (89.94 kJ·mol−1) was
higher than that over 3Co1Zr/SEP (71.46 kJ·mol−1). It was
indicated that the apparent activation energy for β-O-4 bond
breaking could be significantly reduced by using 3Co1Zr/SEP.
4269 https://doi.org/10.1021/acs.energyfuels.3c04637
Energy Fuels 2024, 38, 4256−4272
Energy & Fuels
3.4. Proposing the Pathway of 3Co1Zr/SEP for LCD.
Generally, lignin was initially depolymerized into macro-
molecular fragments under the pyrolysis system, and then, the
breaking of the macromolecular fragments' C−C and C−O
bonds was realized under catalytic action to obtain highly
reactive intermediates.29,32−35 Experimental and character-
ization results showed that Co/SEP possessed the abundant
pores that facilitated the contact of lignin fragments with the
active sites. Additionally, the active Co species promoted the
breakage of lignin C−C and C−O bonds or their derived
macromolecular fragments and simultaneously activated
ethanol to form H* and CH3CH2* species, subsequently
enhancing the hydrogenation and alkylation to obtain
guaiacols and alkylphenols. However, since the Co species in
Co/SEP existed mainly as Co(OH)2, leading to the low
number of LAS and catalyst active sites for breaking C−C and
C−O bonds, therefore, the guaiacol and alkylphenol yields
were lower over Co/SEP. For 3Co1Zr/SEP, it not only had
the abundant pores, but the incorporation of Zr promoted the
transformation of metal hydroxide Co(OH)2 to Co3O4.
Furthermore, it had been found that that the addition of Zr
facilitated the formation of a higher amount of LAS and VO,
which could effectually promote the breakage of lignin C−C
and C−O bonds or their derived macromolecular fragments
and the activation of ethanol to further improve the
hydrogenation and alkylation reaction to obtain more guaiacols
and alkylphenols during LCD. Consequently, under the
synergistic effect between the superior surface area and the
highest LAS and abundant VO, 3Co1Zr/SEP exhibited the
highest yields of guaiacols and alkylphenols. Therefore,
combining the results of the above analysis and discussion,
the reaction pathway for the LCD catalyzed by 3Co1Zr/SEP is
proposed in Scheme 2.
4. CONCLUSIONS
The influence of SEP-supported Co−Zr catalysts with varying
Co/Zr ratios on LCD was examined in this paper. Character-
ization results demonstrated that the addition of Co brought
an abundant pore structure to the catalyst, which facilitated the
contact between the active site and lignin fragments. Moreover,
the addition of Zr species contributed to the conversion of
Co(OH)2 in Co−Zr/SEP and increased LAS and VO.
3Co1Zr/SEP possessed the well pore structure and plenty of
LAS and VO and then exhibited the excellent LCD perform-
ance, in which the optimal yields of guaiacols (445.2 mg/g
lignin) and alkylphenols (109.8 mg/g lignin) were achieved
under the optimal reaction conditions. In addition, it was
demonstrated that 3Co1Zr/SEP significantly reduced the
apparent activation energy for breaking β-O-4 bonds to
71.46 from 89.84 kJ·mol−1 over SEP.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.energyfuels.3c04637.
Additional characterization results for catalysts, detailed
information on GC-MS results for liquid product, and
recyclability experiment details and characterization data
(PDF)
pubs.acs.org/EF Article
■ AUTHOR INFORMATION
Corresponding Authors
Mingqiang Chen − School of Chemical Engineering, Anhui
University of Science and Technology, 232001 Huainan, P.R.
China; orcid.org/0000-0002-1607-8780;
Email: mqchen@aust.edu.cn, hnitchen@163.com
Yishuang Wang − School of Chemical Engineering, Anhui
University of Science and Technology, 232001 Huainan, P.R.
China; Email: yswang@aust.edu.cn, ys_wang1@163.com
Authors
Zinan Zhou − School of Chemical Engineering, Anhui
University of Science and Technology, 232001 Huainan, P.R.
China
Zheng Fang − School of Chemical Engineering, Anhui
University of Science and Technology, 232001 Huainan, P.R.
China
Defang Liang − School of Chemical Engineering, Anhui
University of Science and Technology, 232001 Huainan, P.R.
China
Longyang Li − School of Chemical Engineering, Anhui
University of Science and Technology, 232001 Huainan, P.R.
China
Haosheng Xin − School of Chemical Engineering, Anhui
University of Science and Technology, 232001 Huainan, P.R.
China
Chang Li − School of Chemical Engineering, Anhui University
of Science and Technology, 232001 Huainan, P.R. China;
orcid.org/0000-0001-9857-1765
Gang Yuan − School of Chemical Engineering, Anhui
University of Science and Technology, 232001 Huainan, P.R.
China
Jun Wang − School of Chemical Engineering, Anhui University
of Science and Technology, 232001 Huainan, P.R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.3c04637
Notes
The authors declare no competing financial interest.
M.C. performed supervision, resources and funding acquis-
ition, project administration, and review and editing of the
manuscript. Z.Z. performed investigation, data curation,
writing of the original draft, visualization, validation, and
editing of the manuscript. Y.W. performed supervision,
resources and funding acquisition, visualization, project
administration, and review and editing of the manuscript.
Z.F. performed visualization and software analysis. D.L.
performed data curation and visualization. L.L. performed
software analysis. H.X. performed data curation and editing of
the manuscript. C.L. performed review and editing of the
manuscript. G.Y. performed formal analysis. J.W. performed
visualization.
■ ACKNOWLEDGMENTS
The authors are thankful for financial support from the funds
of the National Natural Science Foundation of China
(22378003, 51906001, and 51876001), the Natural Science
Research Project of Universities in Anhui Province
(KJ2020ZD31), and the Scientific Research Foundation for
High-Level Talents of Anhui University of Science and
Technology. In addition, we are also thankful for the support
4270 https://doi.org/10.1021/acs.energyfuels.3c04637
Energy Fuels 2024, 38, 4256−4272
Energy & Fuels pubs.acs.org/EF
of the characterization analysis technology given by the test
center of Anhui University of Science and Technology.
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