Journal of Analytical and Applied Pyrolysis

Hydrodeoxygenation of lignin-derived oil for alkane fuels using bifunctional Co/HZ-HT

--Manuscript Draft--

Manuscript Number: JAAP-D-23-01216

Article Type: Research Paper

Section/Category: Applied - biomass

Keywords: Co/HZ-HT; Layered double hydroxides; Hydrodeoxygenation; Lignin-derived oil;

Alkane fuel

Abstract: The selective hydrodeoxygenation of lignin-derived oil is an effective pathway for

producing liquid fuels. Here, a series of Co-based catalysts were prepared for
converting lignin-derived phenols into alkane fuels. The effects of cobalt loading, Si/Al
ratio, reaction temperature, time, and pressure on the distributions of alkane fuels were
systematically investigated. The experimental results demonstrated that the in-situ
grown LDH structure in Co/HZ-HT significantly improved the pore structure of the
catalyst, not only enhancing the dispersion of the metallic particles and overall stability
but also strengthening the interaction between the metal and the support. The
complete conversion of guaiacol was achieved, and the selectivity of cyclohexane
reached 97.5% under the conditions of 200 °C, 2 h, 3 MPa H2, and Si/Al ratio of 25.
Co/HZ-HT exhibits excellent hydrogenolysis performance and wide applicability,
outperforming Co/HZ catalysts prepared using conventional impregnation methods. By
extending the feedstock to lignin-derived oil, the complete deoxygenation of the
components and hydrogenation of the aromatic rings were both realized with minimal
side reactions.

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Highlights

Highlights

The Co/HZ-HT catalyst was first prepared with high dispersion and good structure.

The selective hydrodeoxygenation of lignin-derived models and oil with the catalyst

was achieved.

The complete conversion of guaiacol formed a highly selective cyclohexane.

The optimal reaction conditions and possible reaction routes were explored.
Graphical Abstract
Manuscript File Click here to view linked References

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2 Hydrodeoxygenation of lignin-derived oil for alkane fuels using
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5 bifunctional Co/HZ-HT
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7 Kai Wu, Bingbing Luo, Ke Yang, Siyu Wang, Huiyan Zhang*
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10 Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education,
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13 School of Energy and Environment, Southeast University, Nanjing 210096, P.R. China
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16 *Corresponding author. E-mail address: hyzhang@[Link]
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Abstract
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21 The selective hydrodeoxygenation of lignin-derived oil is an effective pathway for
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24 producing liquid fuels. Here, a series of Co-based catalysts were prepared for converting
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27 lignin-derived phenols into alkane fuels. The effects of cobalt loading, Si/Al ratio,
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reaction temperature, time, and pressure on the distributions of alkane fuels were
30
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32 systematically investigated. The experimental results demonstrated that the in-situ grown
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35 LDH structure in Co/HZ-HT significantly improved the pore structure of the catalyst, not
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38 only enhancing the dispersion of the metallic particles and overall stability but also
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strengthening the interaction between the metal and the support. The complete conversion
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43 of guaiacol was achieved, and the selectivity of cyclohexane reached 97.5% under the
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46 conditions of 200 °C, 2 h, 3 MPa H2, and Si/Al ratio of 25. Co/HZ-HT exhibits excellent
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49 hydrogenolysis performance and wide applicability, outperforming Co/HZ catalysts
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prepared using conventional impregnation methods. By extending the feedstock to lignin-
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54 derived oil, the complete deoxygenation of the components and hydrogenation of the
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57 aromatic rings were both realized with minimal side reactions.
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2 Keywords: Co/HZ-HT, Layered double hydroxides, Hydrodeoxygenation, Lignin-
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5 derived oil, Alkane fuel
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7
1. Introduction
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10 Global economic development has been built upon the extensive consumption of
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13 carbon-based fossil fuels in the carbon-economy era, which is primarily used as the main
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16 energy source for electricity, industry, transportation, and heating [1-3]. The escalating
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global energy and environmental crises are driving the transition of energy carriers from
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21 traditional fossil fuels to clean and renewable sources. In the production of energy, fuels,
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24 and chemicals, biomass is widely regarded as a promising and renewable alternative to
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27 fossil fuels [4]. Due to its ability to absorb CO2 through photosynthesis during its growth
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process, biomass is typically considered carbon-neutral, with zero net emissions of carbon
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32 dioxide upon its utilization. Additionally, biomass exhibits broad availability and
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35 enormous reserves [5-6]. Lignocellulosic biomass is mainly composed of polymers such
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38 as cellulose (30-40%), hemicellulose (20-30%), and lignin (15-30%), as well as
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41
extractives like waxes, resins, and inorganic substances [7-9]. Among these, lignin, which
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43 contains naturally occurring unsaturated aromatic ring structures, is a three-dimensional
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46 amorphous polymer consisting of three basic units connected through a series of complex
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49 chemical bonds [10-11]. Currently, over 50 million tons of lignin are left as a by-product
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annually in the paper and pulp industry worldwide [12]. However, the produced lignin is
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54 seriously underutilized since over 98% of it is combusted directly for low-grade heat and
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57 power applications, which causes a huge waste of resources and greenhouse gas (GHG)
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2 emissions [13]. Consequently, it is imperative to develop effective technologies to realize
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5 the valorization of lignin. The carbon efficiency and economic perspectives of the overall
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7 biorefinery process will be greatly improved by fully exploiting the potential of
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10 underutilized lignin, thereby enhancing overall biorefinery competitiveness and reducing
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13 dependence on traditional fossil resources.
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16 Combined with the unique structure of lignin, the production of value-added
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chemicals, such as C6+ alkane, is considered the most suitable and efficient way to utilize
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21 aromatic rings, and this would significantly alleviate the energy crisis [14]. It is worth
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24 noting that hydrodeoxygenation (HDO) is widely regarded as a promising pathway, which
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27 refers to the catalytic upgrading of lignin or its depolymerization products in a
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heterogeneous system. HDO enables the production of high-value hydrocarbon liquid
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32 fuels from lignin, including aromatic and naphthenic products [15]. Aromatic
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35 hydrocarbons are obtained by directly removing the CAr-OH group from phenolic
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38 compounds, while naphthenic products involve both hydrogenation and deoxygenation
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reactions [16-18]. Due to the lowered activation energy for the removal of CAr-OH group
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43 after the hydrogenation of the aromatic ring, lower reaction temperatures were required
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46 in the process of producing naphthene, which facilitates the cleavage of C-O and
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49 suppresses side reactions. Meanwhile, the catalyst plays a crucial role in the selective
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HDO of lignin-derived phenols. It is necessary to rationally design and construct a
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54 bifunctional catalyst with strong hydrogenation and deoxygenation capabilities.
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57 Currently, there are three main types of catalysts commonly used for HDO of lignin-
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2 derived phenols: (1) transition/noble metal-based catalysts, (2) metal oxide catalysts, and
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5 (3) conventional sulfide catalysts, various metal carbides, nitrides, and phosphides [19-
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7 21]. Among them, metal-based catalysts have received extensive research due to their
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10 unique structure and high activity. The supported metal provides active centers for
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13 benzene hydrogenation, while the support provides acidic sites for deoxygenation
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16 reactions [22-27]. Due to the high surface area and abundant acidic sites of zeolites,
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bifunctional metal-based zeolites have emerged as promising catalysts for preparing
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21 target products by HDO. After expanding the catalyst to real lignin, the liquid product
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24 yield was significantly improved and the oxygenated components were converted into
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27 hydrocarbons [28]. Zhang et al. reported that the bifunctional Ru-based zeolites
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effectively catalyzed the HDO of lignin monomers or dimers to produce alkane fuels. The
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32 results showed that the Brønsted acid sites present in the pores of Ru/HZ facilitated the
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35 dehydration reaction, while the metallic function of Ru was responsible for the
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38 hydrogenation of the aromatic rings. Furthermore, a lower Si/Al ratio in HZ led to higher
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selectivity for cyclic alkanes [29]. Meanwhile, catalysts with LDH have revealed
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43 excellent hydrogenation activity and demonstrated significant potential in biomass
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46 conversion [30]. The structural topological transformation of LDH after calcination in a
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49 reducing atmosphere can enhance the dispersion of supported metal particles and overall
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stability [31]. Yue et al. prepared a flower-shaped Ni-based mixed metal oxide (MMO)
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54 catalyst by calcination and reduction of NiZnAl-LDH precursor. The Ni0.5Zn1.5Al1-MMO
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57 catalyst exhibited excellent HDO activity for lignin model compounds at 130 ℃,
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2 outperforming catalysts prepared by impregnation, co-precipitation, and most reported
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5 non-precious metal catalysts [22]. Combining the experimental results and
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7 characterization analyses, the outstanding activity of the catalyst resulted from the
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10 synergistic effects of the specific surface area, metal-support interactions, and acidic sites.
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13 Inspired by these studies, the in-situ hydrothermal growth of CoAl-LDH structure
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16 on HZ with a unique MFI topology was conducted in this work, and the Co/HZ-HT
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catalyst was subsequently prepared through calcination and reduction processes. Various
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21 characterizations were performed to investigate the physicochemical properties of
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24 catalysts, including microstructure, pore structure, distribution of acidic sites, reducibility,
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27 as well as the oxidation state and phase composition of Co particles. The HDO
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performance of Co/HZ-HT catalyst was experimentally explored using guaiacol as the
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32 lignin model compound and was compared with catalysts prepared by the conventional
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35 impregnation method. Additionally, the broad applicability of the Co/HZ-HT catalyst to
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38 other lignin model compounds was verified, and the reaction pathways were investigated
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based on the optimization of catalyst preparation and HDO reaction conditions. Finally,
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43 the catalytic system was extended to real lignin-derived oil, and the HDO performance of
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46 the catalyst was qualitatively analyzed.
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49 2. Materials and methods
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2.1 Materials
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54 HZ with different Si/Al ratios (Si/Al = 25, 38, 50, 85, 130) were provided by Nankai
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57 University Catalyst Co., Ltd. Before experiments, all the fresh catalysts were calcined in
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2 a muffle furnace with an air flow rate of 200 mL/min at 650 ℃ for 5 h to remove the
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5 template and residues. Cobalt (II) nitrate hexahydrate, γ-alumina, guaiacol, phenol, and
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7 diphenyl ether were purchased from Macklin Biochemical Co., Ltd. Cyclohexanol, n-
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10 Hexane, and anisole were purchased from Aladdin Biochemical Technology Co; Ltd.
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13 Isoeugenol, 4-ethylguaiacol, 4-propylguaiacol, and guaiacol methyl ether were purchased
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16 from Meryer Biochemical Technology Co., Ltd. Methanol and urea were purchased from
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Sinopharm Chemical Reagent Co, Ltd. 10% H2/Ar (99.95%), H2 (99.99%), N2 (99.99%)
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21 and He (99.99%) were provided by Nanjing Shangyuan industrial gas plant.
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24 2.2 Catalyst synthesis
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27 Preparation of catalyst precursors by hydrothermal synthesis and taking Co loading
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of 15 wt.% as an example: first, 1.7 g of catalyst support and 60 mL of deionized water
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32 was placed in a 100 mL PTFE-lined container, followed by sonication for 30 minutes.
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35 Next, 1.46 g of Co(NO3)2·6H2O and 2.42 g of urea were added, and the mixture was
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38 stirred at room temperature for 3 h. Then, the PTFE-lined container was sealed and placed
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in a hydrothermal reactor, which was kept at 110 ℃ for 20 h. Subsequently, the solid was
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43 separated by vacuum filtration and dried in a vacuum drying oven at 45 ℃ for 12 h. The
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46 solid powder of CoAl-LDH/HZ was obtained after grinding. Finally, the catalyst
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49 precursor was obtained by heating the solid powder in a muffle furnace with a heating
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rate of 5 ℃/min and holding at 450 ℃ for 5 h under an air atmosphere. The catalysts
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54 prepared by hydrothermal synthesis were named as Co/HZ-HT, of which, unless specified,
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57 the Co loading amount was 15 wt.% and the Si/Al ratio of HZ was 25.
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2 Preparation of catalyst precursors by incipient wetness impregnation: first, 1.7 g of
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5 catalyst support (HZ or Al2O3), 1.46 g of Co(NO3)2·6H2O, and 60 mL of deionized water
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7 were added into a 250 mL flask, followed by magnetic stirring for 24 h. Then, the mixture
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10 was dried using a rotary evaporator at 55 ℃ and 60 rpm for 45 minutes, and subsequently
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13 dried in an oven at 60 ℃ until constant weight. Finally, the obtained solid was ground and
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16 heated in a muffle furnace with a heating rate of 5 ℃/min and held at 450 ℃ for 5 h under
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an air atmosphere to obtain the catalyst precursor. The catalyst prepared by incipient
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21 wetness impregnation was named as Co/HZ or Co/Al2O3.
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24 Reduction of the catalyst: The obtained catalyst precursors were spread evenly in a
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27 quartz boat and placed in a tube furnace. N2 was introduced at a certain flow rate of 200
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mL/min to ensure the air-tightness of the setup. After 10 minutes, the gas was switched
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32 to 10% H2/Ar of 100 mL/min, and the tube furnace was heated at a rate of 5 ℃/min from
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35 room temperature to 450 ℃. After a 4-hour dwell time, the catalyst was naturally cooled
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38 to room temperature and stored under the N2 environment for later use.
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2.3 Catalyst characterizations
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43 High-resolution transmission electron microscopy (TEM) was employed to
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46 characterize the microstructure of the catalysts, as well as the dispersion degree and
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49 crystal morphology of Co particles. The sample was prepared by dispersing the catalyst
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in ethanol and sonicating it for 3 minutes, followed by deposition onto a thin carbon film-
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54 coated copper grid. Additionally, energy-dispersive X-ray spectroscopy was conducted to
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57 analyze the elemental composition (Si, Al, O, and Co) of the Co/HZ-HT catalyst.
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2 The specific surface area, pore volume, and pore size distribution of the catalysts
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5 were determined using a surface area and pore structure analyzer at 77 K through N2
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7 adsorption-desorption isotherm measurements. Prior to the adsorption measurements, the
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10 samples were subjected to in-situ vacuum degassing at 300 ℃ for 6 h. The specific surface
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13 area of the catalysts was calculated using the Brunauer-Emmett-Teller (BET) theory. Both
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16 the micropore area (Smicro) and the micropore volume (Vmicro) were determined using the
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t-plot method, while the total pore volume was obtained using the single-point adsorption
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21 at P/P0=0.99. The average pore diameter was calculated based on the Barrett-Joyner-
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24 Halenda (BJH) adsorption average pore diameter (4V/A) equation.
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27 X-ray diffraction (XRD) analysis was conducted to reveal the crystalline phase
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structure of the catalysts, as well as the phase composition and crystallographic structure
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32 of Co particles. Cu Kα radiation (λ = 1.54187 Å), 40 kV scanning voltage, and 40 mA
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35 scanning current were employed for XRD analysis. And the instrument scanned 2θ from
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38 10 to 80° with a step size of 0.02°. The obtained diffraction patterns were matched against
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the database to identify the phases present in the samples.
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43 X-ray photoelectron spectroscopy (XPS) analysis was performed on the three Co-
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46 based catalysts using an X-ray photoelectron spectrometer equipped with 150 W Al Kα
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49 radiation. The binding energy of the C 1s peak (284.8 eV) was used for charge referencing.
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The chemical states of surface elements in the catalysts were qualitatively determined by
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54 analyzing the peak positions in the spectra.
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57 NH3 temperature-programmed desorption (NH3-TPD) curves were recorded using a
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2 chemisorption analyzer equipped with a thermal conductivity detector (TCD), which was
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5 used to characterize the distribution and strength of acid sites of the catalysts. First, the
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7 samples were heated from room temperature to 400 °C at a rate of 10 °C/min in a 60
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10 mL/min He flow and held for 1 hour. Then, the samples were cooled to 90 °C and
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13 subjected to ammonia adsorption in a 5% NH3/He flow at a flow rate of 50 mL/min until
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16 saturation. Finally, after purging the sample with He at 90 °C for 1 hour, the desorption
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of NH3 was carried out by heating the sample from 90 to 700 °C at a rate of 10 °C/min,
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21 and the desorbed NH3 was quantitatively detected using the TCD.
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24 The reducibility of Co3O4 in precursors of Co-based catalyst was analyzed using a
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27 H2 temperature-programmed reduction (H2-TPR) instrument equipped with a TCD. First,
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0.1 g of the sample was weighed and placed in a U-shaped tube. Then the sample was
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32 heated from room temperature to 400 ℃ at a rate of 10 ℃/min in a 50 mL/min He flow
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35 and held for 2 h. After that, the sample was cooled to 90 ℃ and 10% H2/He at a flow rate
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38 of 50 mL/min was introduced until the baseline stabilized. Finally, the sample was heated
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from 90 ℃ to 700 ℃ at 10 ℃/min in a He flow of 50 mL/min, and the evolved gases were
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43 detected using the TCD.
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46 2.4 Catalytic experiments
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49 HDO of lignin model compounds: the catalytic activity experiments were
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performed in a 50 mL high-pressure reactor. First, 1.0 mmol of lignin model compound,
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54 50.0 mg of catalyst, and 20 mL of n-hexane were added into the autoclave which was
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57 subsequently sealed and connected with hydrogen gas. Then, after purging at atmospheric
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2 pressure for 2 minutes, the pressure was adjusted to 2 MPa. After exchanging H2 for 5
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5 times, the pressure was adjusted to the desired pressure. The reactor was then heated to
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7 the target temperature, and the reaction was carried out for a set time of 0-3 h at 300 rpm.
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10 The reactor was rapidly cooled in an ice-water bath once the reaction was over. After
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13 releasing the pressure, 1 mL of the liquid product, which has been treated with anhydrous
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16 sulfuric acid to remove water and passed through a 0.22 μm organic filter membrane, was
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mixed thoroughly with 19 mL of methanol. Finally, 1 mL of the solution was taken for
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21 analysis using gas chromatography-mass spectrometry (GC-MS, GC: 8890, MS: 5977B,
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24 Agilent, U.S.A.) instrument equipped with an HP-5MS capillary column (30 m × 250 μm
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27 × 0.25 μm) to separate different compounds. High-purity helium was utilized as the
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carrier gas. The temperatures of the injection valve and the transfer line were set at 280
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32 and 240 ℃ respectively. 1 μL of sample was injected and an inlet split ratio of 5:1 was
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35 used. The column oven temperature program was set as follows: hold at 50 ℃ for 3 min,
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38 ramp to 80 ℃ at 3 ℃/min, then ramp to 230 ℃ at 12 ℃/min and hold at 230 ℃ for 5 min.
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After 1.9 min of solvent delay, mass spectra were recorded using electron ionization (EI)
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43 mode with the ionization energy of 70 eV and obtained from 33 to 400 (m/z). The
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46 compositions were determined by the National Institute of Standards and Technology
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49 (NIST) library. The conversion of the reactant and the selectivity of the product can be
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calculated using equations (1) and (2), where PA1 and PA2 represent the peak area of the
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54 substrate before and after the reaction, respectively; PAi and PAtotal represent the peak area
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57 of the target product and all products, respectively.
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 1 PA1 -PA2
2 Conversion(%)= (1)
3 PA1
4 PAi
Selectivity(%) = (2)
5 PAtotal
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7 The typical procedure for lignin oil degradation: Lignin-oil derived from
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10 reductive catalytic fractionation of birch wood in this paper was obtained as follows
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13 conditions of 1.0 g birch wood, 0.1 g Ni/C catalyst, 20 mL methanol, 220 ℃, 2 MPa H2,
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16 3 h, and 750 rpm. 25 mL n-hexane was added into the obtained lignin oil and the mixture
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was sonicated for 30 min for dissolution. Then, 20 mL of the liquid mixture and 0.1 g of
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21 Co/HZ-HT were taken as the substrate. The process of reactor treatment and the analysis
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24 of liquid products remained the same as described above.
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27 3. Results and discussions
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3.1 Characterization analyses of Co-based catalysts
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32 3.1.1 XRD analysis
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35 The XRD characterization results of the catalysts were displayed in Fig. 1. From the
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38 XRD spectrum of HZ, the peaks observed at approximately 8° and 24° (2θ), indicated
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that the catalyst support had a high degree of crystallinity. In the XRD spectra of the three
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43 Co-based catalysts, characteristic peaks were observed at 44.2°, 51.5°, and 75.9° (2θ),
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46 which corresponded to the (111), (200), and (220) crystal planes of Co, respectively, based
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49 on the JCPDS 15-0806 standard card. Meanwhile, Co/HZ and Co/HZ-HT still retained
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the characteristic peaks of HZ, and the intensity of Co characteristic peaks was
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54 significantly higher than that of Co/Al2O3, suggesting a lower loading of metallic Co on
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57 Co/Al2O3. This might be due to the interaction between the metal and the support during
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2 the calcination process, forming difficult-to-reduce CoAl2O4 spinel. In the XRD spectrum
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5 of CoAl-LDH/HZ, characteristic peaks located at 11.5°, 34.6°, and 60.0° (2θ)
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7 corresponded to the CoAl-LDH structure, confirming the in-situ growth of the LDH
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10 structure on the support surface. The XRD characterization results demonstrated the
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13 successful loading of Co metal nanoparticles on the three Co-based catalysts while
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16 retaining the original structure of the support. Additionally, an in-situ growth of the LDH
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structure occurred on the surface of HZ in the preparation process of Co/HZ-HT.
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Co JCPDS#15-0806
21 HZ ¨Co (111) ©Co (200) §Co (220)
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24 Co/Al2O3
¨ © §
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26 ¨
Co/HZ © §
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29 Co/HZ-HT ¨
© §
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31 · LDH
CoAl-LDH/HZ ·
32 ·
·
33 10 20 30 40 50 60 70 80
34 2q (°)
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36 Fig. 1. XRD patterns of HZ, Co/Al2O3, Co/HZ, Co/HZ-HT, and CoAl-LDH/HZ
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39 3.1.2 TEM analysis
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42 In order to further reveal the microstructure of the three Co-based catalysts, as well
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45 as the loading status and crystal morphology of the metal particles, TEM characterization
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47 was performed (Fig. 2). The Co/Al2O3 catalyst exhibited severe metal agglomeration on
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50 its surface. The poor dispersion was attributed to the small specific surface area and lack
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53 of microporous structure of the Al2O3 support, making the wet impregnation method
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56 unfavorable for the dispersion of metal particles [33]. For the Co/HZ catalyst, the metal
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58 particles were well dispersed on the surface and had relatively uniform sizes. This could
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2 be attributed to the higher specific surface area and abundant pore structure of the HZ
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5 support. A comparison between Co/HZ and Co/HZ-HT revealed significant differences
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7 in their microstructures. The surface of Co/HZ-HT was covered by a flocculent substance,
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10 and the dispersion of Co particles was better than that of Co/HZ. This was because the in-
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13 situ growth of the LDH structure occurred on the surface of HZ during the hydrothermal
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16 preparation [30, 32]. Based on the topological transformation of the LDH structure and
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the interaction between metal cations during calcination in a reducing atmosphere, the
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21 dispersion of metal particles at the atomic scale was improved and the anchoring effect
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24 between the metal and the support was enhanced [34-36]. Therefore, Co/HZ-HT exhibited
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27 higher dispersion and stability of the metal particles. Elemental mapping images of
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Co/HZ-HT catalyst further confirmed the highly dispersed nature of Co element. High-
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32 resolution particle lattice images in Fig. 2(a3), (b3), and (c3) revealed lattice fringe
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35 spacing of 0.205 nm, corresponding to the (111) crystal plane of Co, which provided
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38 further evidence supporting the XRD characterization results. Compared to the traditional
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impregnation method, the in-situ growth of the LDH structure in Co/HZ-HT enhanced
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43 the dispersion of metal particles and overall stability.
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36
37
38
39
40
41
42 Fig. 2. TEM images for (a1-a3) Co/Al2O3, (b1-b3) Co/HZ, (c1-c3) Co/HZ-HT, and (d)
43
44
45 HAADF image of Co/HZ-HT and its corresponding EDS elemental mappings of Si, Al,
46
47 O, Co.
48
49
50 3.1.3 XPS analysis
51
52
53 XPS characterization was conducted to further understand the chemical states of Co
54
55
56 species on the surfaces of Co-based catalysts and the Co 2p spectra are demonstrated in
57
58 Fig. 3. The binding energies of Co0 2p3/2 and Co0 2p1/2 were located at 778.7 and 794.8 eV,
59
60
61 14
62
63
64
65
 1
2 respectively. For CoOx 2p3/2, and CoOx 2p1/2, the binding energies were found at 781.3,
3
4
5 and 797.3 eV with the corresponding satellite peaks at 787.3 and 803.3 eV [37,38]. The
6
7 CoOx species mainly included Co3O4, which could be inferred that CoO was the main
8
9
10 constituent of the CoOx species because of the energy difference (6-7 eV) between CoOx
11
12
13 and its satellite peaks in 2p3/2 or 2p1/2. The high abundance of CoOx and its satellite peaks
14
15
16 was attributed to the rapid oxidation of the highly active Co-based catalysts in air, which
17
18
formed a passivation layer on the surface [39]. Furthermore, compared to Co/Al2O3, both
19
20
21 Co/HZ and Co/HZ-HT exhibited a positive shift in the binding energy of Co 2p, with a
22
23
24 larger shift observed for the latter, indicating an enhanced interaction between the metal
25
26
27 and the support [32]. The XPS characterization results confirmed the presence of Co
28
29
particles on the catalyst surface and also demonstrated that the in-situ growth of the LDH
30
31
32 structure in Co/HZ-HT enhanced the interaction between the metal and the support.
33
34
35 Co/Al2O3 Co 2p1/2 Co 2p3/2
36
37
38
39
Co/HZ
40
41
42 Satellite Satellite
43 Peak CoOx Co0 Peak CoOx Co0
44 Co/HZ-HT
45
46
47
48
49 810 805 800 795 790 785 780 775
50
51
52
Fig. 3. Co 2p XPS spectra of Co/Al2O3, Co/HZ, and Co/HZ-HT
53
54 3.1.4 Specific surface area and pore structure analysis
55
56
57 The pore structure of catalysts had a significant impact on their catalytic activity.
58
59
60
61 15
62
63
64
65
 1
2 Specific surface area and pore structure analysis were conducted to further explore the
3
4
5 pore structure of the catalysts. The N2 adsorption-desorption isotherms and pore size
6
7 distribution curves were signified in Fig. 4(a) and (b), respectively, and the typical
8
9
10 properties were summarized in Table 1. From Fig. 4(a), it could be observed that all four
11
12
13 catalysts exhibited typical Type IV adsorption-desorption isotherms and H4 hysteresis
14
15
16 loops, indicating the presence of mesoporous structures [40]. Combined with the pore size
17
18
distribution curves and typical properties, the following conclusions could be drawn: (1)
19
20
21 Co/Al2O3 had a relatively low specific surface area and a wide pore size distribution in
22
23
24 the mesoporous range, indicating the predominance of mesoporous structures. (2) HZ
25
26
27 support was mainly composed of microporous structures, with a small portion of
28
29
mesoporous structures and a narrow pore size distribution in the mesoporous range. (3)
30
31
32 Compared to the HZ catalyst, the introduction of Co particles through the hydrothermal
33
34
35 method led to a slight decrease in SBET and Vmicro but generated a more evenly distributed
36
37
38 mesoporous structure. This was because the introduction of Co nanoparticles blocked
39
40
41
some of the micropores, resulting in a decrease in the micropore structure parameters.
42
43 However, the in-situ growth of the LDH structure in Co/HZ-HT introduced uniform
44
45
46 mesopores, significantly improving the pore structure [41].
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61 16
62
63
64
65
 1
2 (a) (b)
HZ
HZ 0.08
3 150 Co/Al2O3
Quantity Adsorbed (cm³/g STP)

dV/dD Pore Volume (cm³/g·nm)

Co/Al2O3
4 Co/HZ
Co/HZ
Co/HZ-HT
5 Co/HZ-HT 0.06

6 100
7 0.04
8
9
0.02
10 50

11
12 0.00
13 0
14 0.0 0.2 0.4 0.6 0.8 1.0 1 10 100
Relative Pressure (P/P0) Pore Diameter (nm)
15
16
17 Fig. 4. N2 adsorption-desorption isotherms (a) and pore-size distributions of HZ,
18
19
20 Co/Al2O3, Co/HZ, and Co/HZ-HT(b).
21
22
23 Table 1. The typical properties of HZ, Co/Al2O3, Co/HZ, and Co/HZ-HT.
24
25 SBETa Smicrob Vmicrob Vtotalc Pore Sized
Sample
26 (m²/g) (m²/g) (cm3/g) (cm3/g) (nm)
27
28 HZ 293.00 218.48 0.09 0.17 5.20
29 Co/Al2O3 121.21 0.00 0.00 0.19 5.92
30 Co/HZ 306.61 213.01 0.08 0.19 7.01
31
32 Co/HZ-HT 309.70 215.77 0.09 0.24 7.71
33 a
Calculated by the BET method.
34 b
35 Derived by the t-plot method.
c
36 Determined by the single point adsorption at P/P0 = 0.99.
37 d
Calculated by the BJH Adsorption average pore diameter (4V/A).
38
39
3.1.5 NH3-TPD analysis
40
41
42 The distribution and concentration of acid sites in catalysts had a significant impact
43
44
45 on their HDO activity. The results of NH3-TPD analysis were disclosed in Fig. 5 and the
46
47
48 acid site statistics were summarized in Table 2. Generally, the desorption peaks of NH3 at
49
50
51
low temperatures (<300 ℃) were related to weak acid sites, those at medium temperatures
52
53 (300-500 ℃) were related to medium-strong acid sites, and those at high temperatures
54
55
56 (>500 ℃) depending on strong acid sites [42,43]. It could be observed from the NH3-TPD
57
58
59 curves that, compared to HZ, Co/HZ exhibited a significant decrease in the peak intensity
60
61 17
62
63
64
65
 1
2 of NH3 desorption in the low and medium temperature regions, while Co/HZ-HT showed
3
4
5 a slight decrease. This indicated that the introduction of Co nanoparticles covered some
6
7 of the acid sites on the support, and the LDH structure to some extent reduced the
8
9
10 coverage. It is worth noting that Co/HZ-HT exhibited a new NH3 desorption peak at high
11
12
13 temperatures, which might be attributed to the strong interaction between Co0 and the
14
15
16 support [44]. According to the quantitative results of acid site concentration (Table 2), the
17
18
total acidity of the three Co-based catalysts followed the ascending order of Co/Al2O3,
19
20
21 Co/HZ, and Co/HZ-HT.
22
23
24 < 300 ℃ 300-500 ℃ > 500 ℃
25 HZ
26
27
28 Co/Al2O3
29
30
31
32 Co/HZ
33
34
35 Co/HZ-HT
36
37 100 200 300 400 500 600
38 Temperature (℃ )
39
40
41
Fig. 5. NH3-TPD curves of HZ, Co/Al2O3, Co/HZ, and Co/HZ-HT.
42
43 Table 2 Concentration of acidic sites of HZ, Co/Al2O3, Co/HZ, and Co/HZ-HT.
44
45 Quantity Desorbed (mmol/g)
46 Sample
47 <300 ℃ 300-500 ℃ >500 ℃
48 HZ 2.24 0.57 0.00
49
50 Co/Al2O3 1.00 0.36 0.00
51 Co/HZ 1.40 0.38 0.00
52
Co/HZ-HT 1.54 0.58 0.17
53
54
55 3.1.6 H2-TPR analysis
56
57
The reducibility of Co3O4 in the precursors of catalysts was investigated using H2-
58
59
60
61 18
62
63
64
65
 1
2 TPR analysis, as shown in Fig. 6. Generally, the reduction process of Co3O4 was
3
4
5 temperature-dependent: (1) < 250 ℃, almost no reduction reaction occurs; (2) 250-300 ℃,
6
7 Co3O4 can be reduced to CoO, resulting in a mixture of CoO and Co3O4 phases; (3) >
8
9
10 300 ℃, CoO was further reduced to metallic Co. Moreover, a shift of the reduction
11
12
13 temperature towards lower temperatures indicates that the precursor of the catalyst is
14
15
16 more easily reducible, suggesting a stronger interaction between the metal oxide and the
17
18
support [45]. It can be observed from Fig. 6 that the precursor of Co/Al2O3 exhibited a
19
20
21 small H2 consumption at low temperatures and a strong signal peak above 500 ℃,
22
23
24 indicating that the precursor of this catalyst was difficult to reduce, possibly due to the
25
26
27 formation of CoAl2O4 spinel during calcination [46, 47]. Compared to Co/HZ, the
28
29
precursor of Co/HZ-HT showed a much higher H2 consumption at low temperatures and
30
31
32 the peak of the highest intensity presented a clear shift towards lower temperatures.
33
34
35 Additionally, the reduction of CoO to Co0 at 320 ℃ was more pronounced. These
36
37
38 observations indicated that the hydrothermal-synthesized Co/HZ-HT exhibited stronger
39
40
41
metal-support interaction than the traditional-synthesized Co/HZ. It was likely attributed
42
43 to the in-situ growth of the LDH structure, which enhanced the interaction between the
44
45
46 metal and the support, thereby improving the catalytic activity of the catalyst.
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61 19
62
63
64
65
 1
2
3 280 ℃ Co/Al2O3
4
5
6 235 ℃ 320 ℃ 500 ℃
7
8 Co/HZ
9
10
11
12
13 Co/HZ-HT
14
15 100 200 300 400 500 600
16 Temperature (℃ )
17
18
Fig. 6. H2-TPD curves of precursors of Co/Al2O3, Co/HZ, and Co/HZ-HT.
19
20
21 3.2 Catalytic activity of Co-based catalysts
22
23
24 To investigate the catalytic activity of different catalysts in the HDO of guaiacol, a
25
26
27 series of comparative experiments were conducted under the reaction conditions of 200 ℃,
28
29
3 MPa H2, and 2 h. As shown in Table 3, guaiacol was almost unconverted without a
30
31
32 catalyst. The conversion of guaiacol over the HZ support was only 10.1%, with a
33
34
35 selectivity of 90.9% towards cyclohexane, indicating that the acidic sites alone were
36
37
38 insufficient for the efficient conversion of guaiacol. It could be found from entry 3 that
39
40
41
the conversion of guaiacol reached 100.0% over Co/Al2O3, but cyclohexane was hardly
42
43 formed, leading to cyclohexanol as the main product with a selectivity as high as 99.3%.
44
45
46 This phenomenon suggested that Co/Al2O3 facilitated the hydrogenation of the benzene
47
48
49 ring and the removal of CAr-OCH3, but struggled to further deoxygenate cyclohexanol to
50
51
52
cyclohexane. This was because the HDO reaction required not only metallic species to
53
54 provide active sites for hydrogenation reactions but also the supports to provide acidic
55
56
57 sites for the removal of hydroxyl groups [23,48]. According to the characterization results
58
59
60
61 20
62
63
64
65
 1
2 from NH3-TPD, Co/Al2O3 showed a poor performance in the distribution and
3
4
5 concentration of acid sites. For the Co/HZ catalyst in entry 4, the conversion of guaiacol
6
7 and the selectivity towards cyclohexane reached 100.0% and 77.3%, respectively. The
8
9
10 HZ support in Co/HZ possessed more acidic sites than Co/Al2O3, which provided certain
11
12
13 deoxygenation activity and promoted the conversion of cyclohexanol to cyclohexane. As
14
15
16 for Co/HZ-HT, the conversion of guaiacol reached 100.0%, with a selectivity towards
17
18
cyclohexane as high as 97.5%, and there was no cyclohexanol detected in the final
19
20
21 products. Co/HZ-HT exhibited enhanced HDO performance compared to Co/HZ,
22
23
24 achieving complete hydrogenation and deoxygenation of the substrate. This could be
25
26
27 attributed to the fact that the in-situ growth of LDH structure enhanced the dispersion of
28
29
metal particles and overall stability, which strengthened the metal-support interaction and
30
31
32 reduced the coverage of acidic sites, thereby improving the HDO performance.
33
34
35
Table 3 Catalytic performance in the HDO of guaiacol over different catalysts
36 Sel. (%)
37
38
39 Entry Catalyst Conv. (%)
40
41
42
43 1 None 4.3 0.0 0.0 100.0
44
2 HZ 10.1 90.9 9.1 0.0
45
46 3 Co/Al2O3 100.0 0.0 0.7 99.3
47 4 Co/HZ 100.0 77.3 3.2 19.5
48
49 5 Co/HZ-HT 100.0 97.5 2.5 0.0
50 a
Reaction condition: 1.0 mmol (125.4 mg) of guaiacol, 50.0 mg of catalyst, 20 mL of n-hexane as the
51
solvent, 200 ℃, 600 rpm, 2 h, and 3 MPa H2 at RT.
52
53
54 Additionally, as shown in Table S1, the bifunctional Co/HZ-HT catalyst in this work
55
56 could selectively convert guaiacol into cyclohexane under relatively mild conditions. To
57
58
59 verify the wide applicability of the Co/HZ-HT, HDO experiments were conducted on
60
61 21
62
63
64
65
 1
2 lignin monomers and dimers containing various functional groups, and the results were
3
4
5 expressed in Table 4. All lignin model compounds were completely converted with a high
6
7 selectivity towards cyclic hydrocarbons and minimal side reactions, indicating the high
8
9
10 HDO activity and broad applicability of Co/HZ-HT.
11
12 Table 4 HDO results of other lignin model compounds
13
14 Entry Substrate Conv. (%) Sel. (%)
15
16
17
18 1 100.0
19
20 99.1 0.9
21
22
23 2 100.0
24
25 94.7 1.0 4.3
26
27
28
29 3b 100.0
30
31 98.4 1.0 0.6
32
33
34 4 100.0
35
36 96.9 0.7 2.4
37
38
39
40 5 100.0
41
42 96.0 3.3 0.7
43
44
45 6 100.0
46
47 99.3 0.4 0.2 0.1
48
49
50
51 7 100.0
52
53 97.3 1.6 0.1 1.0
54
55
56 8b 100.0
57
58 93.2 4.8 1.5 0.5
59
60
61 22
62
63
64
65
 1 Reaction condition: 1.0 mmol of model compound, 50.0 mg of Co/HZ-HT, 20 mL of n-hexane as the
2
3 solvent, 600 rpm, 3 MPa H2 at RT, 2 h, 200 ℃a, and 220 ℃b.
4
5 3.3 Effect of catalyst preparation conditions on alkane fuels
6
7
8 The optimal catalyst preparation conditions were studied by investigating the
9
10
11 influence of different Co loadings and Si/Al ratios of HZ on the catalytic performance of
12
13
14
Co/HZ-HT. It can be seen from Fig. 7(a) that, as the Co loading increased from 0 to 15
15
16 wt.%, the conversion rate of guaiacol linearly increased from 10.1% to 100.0% and the
17
18
19 selectivity to cyclohexane increased from 90.9% to 97.5%, while the yield of
20
21
22 cyclohexanol remained at 0. This was because the active sites for hydrogenation were
23
24
25
limited when the Co loading was relatively low, and guaiacol could not be completely
26
27 converted to cyclohexanol which would rapidly undergo a dehydroxylation reaction to
28
29
30 form cyclohexane. With further increase in the Co loading, the conversion rate of guaiacol
31
32
33 stabilized at 100.0% and the selectivity to cyclohexane slightly decreased, while the
34
35
36
selectivity to methyl-cyclopentane slightly increased. Previous studies had indicated that
37
38 the particle size of Co nanoparticles increased with increasing Co loading amount, and
39
40
41 the catalytic activity depended not only on the metal loading but also on the size of the
42
43
44 metal particles. Therefore, when the Co loading increased from 15 to 25 wt.%, the
45
46
47
increase in Co particle size enhanced the isomerization (ISO) of cyclohexanol to
48
49 cyclopentyl-methanol, which further dehydroxylated to form methyl-cyclopentane,
50
51
52 leading to a decrease in the selectivity to cyclohexane. Accordingly, 15 wt.% of Co
53
54
55 loading provided a higher Co content and moderate particle size, resulting in optimal
56
57
58
HDO activity. It could be seen from Fig. 7(b) that, as the Si/Al ratio of HZ increased from
59
60
61 23
62
63
64
65
 1
2 25 to 130, the conversion rate of guaiacol stabilized at 100.0% and the selectivity to
3
4
5 cyclohexane showed a decreasing-then-increasing trend, while the selectivity to
6
7 cyclohexanol exhibited the opposite trend. In conclusion, the optimal conditions for the
8
9
10 catalyst preparation were determined as 15 wt.% of Co loading and 25 of Si/Al ratio.
11
12 (a) (b)
100 100
13
14

Conversion & Selectivity (%)

Conversion & Selectivity (%)

80 80
15
16
60 Guaiacol conversion 60 Guaiacol conversion
17 Cyclohexane Cyclohexane
18 Methylcyclopentane Methylcyclopentane
40 40
19 Cyclohexanol Cyclohexanol
20
20 20
21
22
0 0
23
24 0 10 15 20 25 25 38 50 85 130
Co loading (wt.%) Si/Al ratio of HZ
25
26
27 Fig. 7. Effect of different (a) Co loadings (Si/Al = 25) and (b) Si-to-Al ratios (Co loading
28
29
30 = 15 wt.%) on the HDO of guaiacol over Co/HZ-HT. (Reaction condition: 1.0 mmol
31
32
33 (125.4 mg) of guaiacol, 50.0 mg of catalyst, 20 mL of n-hexane as the solvent, 200 ℃,
34
35
36
600 rpm, 2 h, and 3 MPa H2 at RT)
37
38 3.4 Effect of reaction conditions on alkane fuels
39
40
41
42
The optimal reaction conditions were investigated by studying the influence of
43
44 reaction temperature, reaction time, and H2 pressure on the catalytic performance of
45
46
47 Co/HZ-HT. As shown in Fig. 8(a), the conversion of guaiacol linearly increased from 4.1%
48
49
50 to 100.0% when the temperature increased from 140 to 200 ℃. With further increase in
51
52
53 the temperature, the conversion rate of guaiacol remained at 100.0% and the selectivity
54
55 to cyclohexane slightly decreased, while the selectivity to methyl-cyclopentane slightly
56
57
58 increased. Temperature mainly affected the catalytic activity of the catalyst. The substrate
59
60
61 24
62
63
64
65
 1
2 cannot be fully converted because of the poor catalytic activity at a lower temperature.
3
4
5 Although a much higher temperature would achieve complete conversion, side reactions,
6
7 and catalyst coking were also enhanced at the same time. Fig. 8(b) presented the results
8
9
10 at different reaction times and it is worth noting that, with a reaction time of 0.5 h, the
11
12
13 conversion of guaiacol reached 97.8% and the selectivity to cyclohexane was as high as
14
15
16 96.3%. Furthermore, there were no detectable by-products except for the absence of
17
18
methyl-cyclopentane, indicating fewer side reactions in the current system. When the
19
20
21 reaction time increased to 2 h, the selectivity to cyclohexane reached its maximum value
22
23
24 of 97.5%. However, with a further increase in time, the selectivity to cyclohexane slightly
25
26
27 decreased, while the selectivity to methyl-cyclopentane slightly increased. This indicated
28
29
another pathway for the formation of methyl-cyclopentane, which was the ISO of
30
31
32 cyclohexane to methyl-cyclopentane. According to the HDO results at different initial H2
33
34
35 pressures presented in Fig. 8(c), when the pressure increased from 0.1 to 4 MPa, the
36
37
38 conversion of guaiacol linearly increased and then stabilized at 100.0%. The selectivity
39
40
41
to cyclohexane continuously increased, while the selectivity to methyl-cyclopentane
42
43 continued to decrease. This demonstrated that the increase in reaction pressure had a
44
45
46 certain inhibitory effect on side reactions. In conclusion, the optimal reaction conditions
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61 25
62
63
64
65
 1
2 for the catalytic HDO of guaiacol over Co/HZ-HT were 200 ℃, 2 h, and 4 MPa.
3
4
5 (a) (b) (c)
6 100 100 100

Conversion & Selectivity (%)

Conversion & Selectivity (%)

Conversion & Selectivity (%)

80 80 80
8
9 60 60 Guaiacol conversion
Cyclohexane
60 Guaiacol conversion
Cyclohexane
10 40
Guaiacol conversion
Cyclohexane 40
Methylcyclopentane
40
Methylcyclopentane
Cyclohexanol Cyclohexanol
11 Methylcyclopentane
Cyclohexanol
12 20 20 20

13 0 0 0
14 140 160 180 200 220 0 0.5 1 2 3 0.1 1 2 3 4
15 Temperature (℃ ) Reaction time (h) H2 pressure (MPa)

16
17 Fig. 8. Effect of different (a) temperatures, (b) reaction time, and (c) H2 pressure on the
18
19
20 HDO of guaiacol over Co/HZ-HT. (Reaction condition: 1.0 mmol (125.4 mg) of guaiacol,
21
22 50.0 mg of catalyst, 20 mL of n-hexane as the solvent, and 600 rpm)
23
24
25 3.5 Proposed pathway for HDO of guaiacol
26
27
28 Possible reaction pathways for HDO of guaiacol were proposed based on the
29
30
31 experimental results (Fig. 9). Without the addition of catalysts, cyclohexanol was mainly
32
33 produced by hydrodeoxygenation of guaiacol. The HDO of guaiacol over the HZ catalyst
34
35
36 first formed the 2-methoxycyclohexanol, and then the cyclohexane was formed by
37
38
39 dehydroxylation and demethoxylation. The HDO of guaiacol over Co/Al2O3 catalyst first
40
41
42 produced phenol by demethoxylation and then formed the cyclohexanol by hydrogenation.
43
44 The HDO of guaiacol with Co/HZ catalyst was firstly demethoxylated to phenol and then
45
46
47 hydrogenated to cyclohexanol. Most of the cyclohexanol was further converted to
48
49
50 cyclohexane by dehydroxylation. There were two main ways for hydrodeoxidation of
51
52
53 guaiacol with Co/HZ-HT catalyst. (1) Guaiacol was first hydrogenated to produce 2-
54
55 methoxycyclohexanol, and then dehydroxylation and demethoxylation to produce
56
57
58 cyclohexane. (2) Guaiacol was demethoxylated to anisole, then hydrogenated to
59
60
61 26
62
63
64
65
 1
2 methoxycyclohexane, and finally cleaved to cyclohexane by ether bonds. A small amount
3
4
5 of cyclohexanol was produced by the ectopic reaction of methylcyclopentane.
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Fig. 9. Proposed reaction pathways in HDO of guaiacol with/without catalysts
33
34
35 3.6 Direct conversion of lignin oil to alkane fuels
36
37
38 The substrate was extended to real lignin oil based on the excellent results of the
39
40
41
lignin model compounds. As shown in Fig. 10(a), the detectable products in lignin oil
42
43 mainly included 4-propylguaiacol, 4-propylsyringol, 4-propylguaiacolol, and 4-
44
45
46 propylsyringolol, while compounds (1-3) were impurities in the n-hexane solvent. The
47
48
49 results under the conditions of 280 ℃ and 6 h were pointed in Fig. 10(b), where it could
50
51
52
be observed that the main components of lignin oil have undergone complete
53
54 deoxygenation and hydrogenation. Meanwhile, propyl-cyclohexane hold a dominant
55
56
57 position among the limited variety of products, which was consistent with the dominance
58
59
60
61 27
62
63
64
65
 1
2 of propyl- or propylol- compounds in lignin oil, indicating fewer side reactions in the
3
4
5 HDO process. The results of the reaction at more severe conditions of 300 ℃ and 20 h are
6
7 revealed in Fig. 10(c). It could be observed that there were partially unsaturated aromatic
8
9
10 hydrocarbons in the products, and the yields of cycloalkanes are much higher than those
11
12
13 in Fig. 10(b). This might be attributed to the fact that the solvent n-hexane participated in
14
15
16 the reaction under severe conditions owing to the selective aromatization of the HZ
17
18
support.
19
20
21 Before
(a) HDO
22 5
23 1 7
24 4
25 6
23
26
27 2 4 6 8 10 12 14
28 Retention (min)
29 After
30 (b) 9 HDO
31 1
32
33 2 6 7 10
3 4 5 8
34
35
2 4 6 8 10 12 14
36
37
Retention (min)
12 After
38 (c) 16 HDO
34
39 1 7
8 9 10 14 17
40 5 13
41
2 6 11 15 181920
42
43
44 2 4 6 8 10 12 14
45 Retention (min)
46
47 Fig. 10. Total ion chromatograms of the products from (a) the reductive catalytic
48
49
50 fractionation of birch wood over Ni/C, (b) the HDO of lignin oil over Co/HZ-HT
51
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53 (Reaction condition: 100.0 mg catalyst, 280 ℃, 600 rpm, 6 h, and 5 MPa H2 at RT), and
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56 (c) the HDO of lignin oil over Co/HZ-HT (Reaction condition: 100.0 mg catalyst, 300 ℃,
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58 600 rpm, 20 h, and 3 MPa H2 at RT)
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2 4. Conclusions
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5 Co-based zeolite catalysts with LDH structure were designed and prepared in this
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7 work, which was applied to HDO of lignin model compounds and lignin-derived oil. The
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10 results indicated that all Co-based catalysts were successfully synthesized and the
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13 structure of the catalyst support was retained. The in-situ grown LDH structure
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16 significantly improved the pore structure of Co/HZ-HT, improving the dispersion of metal
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particles and the overall stability of the catalyst. Additionally, new strong acid sites were
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21 also introduced and the interaction between the metal and the support was enhanced. Then,
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24 Co/HZ-HT demonstrated excellent HDO performance, achieving complete conversion of
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27 guaiacol under relatively mild conditions (200 ℃, 2 h, and 3 MPa). The selectivity of
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cyclohexane reached 97.5%, with only a minor byproduct, methyl-cyclopentane. These
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32 results are better than the Co/HZ catalysts prepared by the traditional impregnation
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35 method. Then, the catalyst preparation (Co loading and Si/Al of HZ) and reaction
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38 conditions (temperature, time, and pressure) were optimized. The Co/HZ-HT also
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exhibited excellent catalytic performance in the HDO of other lignin model compounds
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43 and lignin-derived oil into alkane fuels, showing the broad applicability of the catalyst.
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46 CRediT authorship contribution statement
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49 Kai Wu: the idea of the experiment, experiment conduction, and manuscript writing;
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Bingbing Luo: experiment conduction; Ke Yang: characterizing experiment; Siyu Wang:
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54 analysis of XPS and TEM; Huiyan Zhang: the design of the experiment, manuscript
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57 editing, revisions, and theory guidance.
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61 29
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 1
2 Acknowledgements
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5 This work was supported by the National Natural Science Fund for Excellent Young
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7 Scholars (Grant No. 51822604).
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10 References
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Declaration of Interest Statement

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: