Hydrodeoxygenation of guaiacol to phenol using endogenous hydrogen induced by chemo-splitting of water over a versatile nano-porous Ni catalyst

Ren, Xiaohong; Sun, Zhuohua; Lu, Jiqing; Cheng, Jinling; Zhou, Panwang; Yu, Xiaoqiang; Rong, Zeming; Li, Changzhi

doi:10.1039/d2gc04340h

Cited by 24 publications

(24 citation statements)

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“…This might be responsible for a slight decrease of the activity of catalyst. 11,67 The catalyst after the cycle was recalcined and then applied for the sixth reaction. It was concluded that the catalytic performance of Ni/20% CeO 2 −C-500 was restored.…”

Section: Catalyst Reusabilitymentioning

confidence: 99%

“…Both the active metal and support are necessary in the catalytic system. A range of Ni-based catalysts that were explored by researchers ascribe to excellent cracking performance and low-cost advantages. , He et al investigated a conversion mechanism of lignin model compounds over Ni/SiO 2 . Wang et al studied that most of lignin was cleaved to phenols by the catalytic hydrogenolysis over a Ni–Mo 2 C catalyst at 250 °C and 2 MPa H 2 .…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Conversion of Lignin and Lignin-Derived β-O-4 Ether to Cyclohexanols over a CeO₂-Doped Carbon-Supported Nickel-Based Catalyst

Xie,

Zhao,

et al. 2024

ACS Sustainable Chem. Eng.

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In this study, a CeO 2 -doped carbon-supported nickel-based catalyst (Ni/XCeO 2 −C−Y) was synthesized and applied to the catalytic depolymerization of lignin and its derivatives. The variations in CeO 2 content and calcination temperature are observed to cause a notable impact on the existence of oxygen vacancies. The results demonstrated that an optimal Ni/20%CeO 2 − C-500 exhibited excellent effectiveness in the cleavage of the β-O-4 bond to ethylbenzene and cyclohexanol at 180 °C and 1 MPa N 2 . In this system, isopropanol is used as a hydrogen-donating solvent as it can produce H 2 (detected by GC) during the reaction. The successful doping of CeO 2 onto carbon contributes to the formation of an interaction between the carrier and nickel, causing a more uniform dispersion of metallic Ni. In addition, the selectivity of phenols in the real lignin depolymerization decreased from noncatalytic 71.5 to 25.4%, and most of the phenols were well converted into cyclohexanols and ketones. The reusability experiments revealed that Ni/20%CeO 2 −C-500 possessed excellent recycling and regeneration properties.

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Section: Catalyst Reusabilitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Catalytic Conversion of Lignin and Lignin-Derived β-O-4 Ether to Cyclohexanols over a CeO₂-Doped Carbon-Supported Nickel-Based Catalyst

Xie,

Zhao,

et al. 2024

ACS Sustainable Chem. Eng.

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“…Ni/Fe/Co as non-noble metals will be partially oxidized after dissociation of water. 19 To make the characterization results more accurate, we pretreated the catalyst in water at 180 °C for 2 h as a comparison (denoted as RuNi (Fe/Co)-treated). The in situ DRIFTS spectra of CO adsorption were obtained to investigate the chemical state of Ru (Figure 5).…”

Section: Characterization Of the Real Active Site In The Reactionmentioning

confidence: 99%

“…Lignin, as one of the three major components of lignocellulose, contains massive methoxylated phenylpropanoid, which is very promising for the preparation of phenols. ,− In recent years, multiple catalysts and reaction systems have been created to hydrodeoxygenate phenols, derived from lignin, such as guaiacol and 4-propylguaiacol, into phenols. − However, all of these systems suffer from the same problem, that is, the harsh reaction conditions and high hydrogen consumption. Very recently, Li and co-workers developed a versatile nanoporous Ni catalyst that can efficiently hydrodeoxygenate guaiacol to phenol in the absence of exogenous hydrogen by chemically splitting water . However, the study was limited to only lignin model compounds, and the reaction results of real lignin or lignin oil are not clear.…”

Section: Introductionmentioning

confidence: 99%

“…Very recently, Li and co-workers developed a versatile nanoporous Ni catalyst that can efficiently hydrodeoxygenate guaiacol to phenol in the absence of exogenous hydrogen by chemically splitting water. 19 However, the study was limited to only lignin model compounds, and the reaction results of real lignin or lignin oil are not clear. In our previous works, we could produce 4alkylphenols (mainly 4-ethylphenol) from lignin and lignin oils using hydrogenolysis driven by self-reforming.…”

Section: Introductionmentioning

confidence: 99%

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Selective Production of 4-Propylphenol from Lignin Oil without Exogenous Hydrogen over a RuNi/NiAl₂O₄ Catalyst

Zhou,

Song,

Guo

et al. 2023

ACS Sustainable Chem. Eng.

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Recently, the depolymerization of lignocellulosic biomass without exogenous hydrogen sources (named self-hydrogen supplied catalytic fractionation, SCF) was realized under mild conditions, with nearly theoretical yield of lignin phenolic monomers (lignin oil) achieved (Zhou et al., JACS Au, 2023, 3, 1911−1917. Herein, we further developed a new process for the demethoxylation of thus-prepared lignin oil to get 4-propylphenol in the absence of exogenous hydrogen over the RuNi/ NiAl 2 O 4 catalyst. In this process, a hint of hydrogen is generated by the splitting of water on the Ni surface, which drives the removal of methoxy groups in lignin oil and produces 4-alkylphenol and methanol, and then the following aqueous phase reforming of methanol supplies more hydrogen and accelerates the entire reaction. Interestingly, water splitting on the Ni surface forms a Ru-NiO x interface, which can improve the C−O bond activation ability and facilitate the removal of methoxy groups. In addition, Ru in Ru-NiO x species is more metallic, which is beneficial for the aqueous phase methanol reforming. Under optimized conditions, 17.0 wt % yield of 4-propylphenol could be acquired in real birch lignin oil. This strategy efficiently produces 4-propylphenol from lignin oil using structural hydrogen in both lignin oil and H 2 O. The result is a promising and effective approach for lignin oil upgrading.

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Selective Cleavage of C_β−O−4 Bond for Lignin Depolymerization via Paired‐Electrolysis in an Undivided Cell

Huang,

Yu,

Guo

et al. 2024

Angewandte Chemie

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The cleavage of C‐O bonds is one of the most promising strategies for lignin‐to‐chemicals conversion, which has attracted considerable attention in recent years. However, current catalytic system capable of selectively breaking C‐O bonds in lignin often requires a precious metal catalyst and/or harsh conditions such as high‐pressure H2 and elevated temperatures. Herein, we report a novel protocol of paired electrolysis to effectively cleave the Cβ‐O‐4 bond of lignin model compounds and real lignin at room temperature and ambient pressure. For the first time, “cathodic hydrogenolysis of Cβ‐O‐4 linkage” and “anodic C‐H/N‐H cross‐coupling reaction” are paired in an undivided cell, thus the cleavage of C‐O bonds and the synthesis of valuable triarylamine derivatives could be simultaneously achieved in an energy‐effective manner. This protocol features mild reaction conditions, high atom economy, remarkable yield with excellent chemoselectivity, and feasibility for large‐scale synthesis. Mechanistic studies indicate that indirect H* (chemical absorbed hydrogen) reduction instead of direct electron transfer might be the pathway for the cathodic hydrogenolysis of Cβ‐O‐4 linkage.

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Hydrodeoxygenation of guaiacol to phenol using endogenous hydrogen induced by chemo-splitting of water over a versatile nano-porous Ni catalyst

Abstract: In this work, an innovative route for upgrading biomass-derived phenolic monomers by "hydrogen-free" hydrodeoxygenation (HDO) was proposed and evaluated. The HDO process was integrated with the activation of water and...

Cited by 24 publications

References 65 publications

Catalytic Conversion of Lignin and Lignin-Derived β-O-4 Ether to Cyclohexanols over a CeO₂-Doped Carbon-Supported Nickel-Based Catalyst

Catalytic Conversion of Lignin and Lignin-Derived β-O-4 Ether to Cyclohexanols over a CeO₂-Doped Carbon-Supported Nickel-Based Catalyst

Selective Production of 4-Propylphenol from Lignin Oil without Exogenous Hydrogen over a RuNi/NiAl₂O₄ Catalyst

Selective Cleavage of C_β−O−4 Bond for Lignin Depolymerization via Paired‐Electrolysis in an Undivided Cell

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Hydrodeoxygenation of guaiacol to phenol using endogenous hydrogen induced by chemo-splitting of water over a versatile nano-porous Ni catalyst

Abstract: In this work, an innovative route for upgrading biomass-derived phenolic monomers by "hydrogen-free" hydrodeoxygenation (HDO) was proposed and evaluated. The HDO process was integrated with the activation of water and...

Cited by 24 publications

References 65 publications

Catalytic Conversion of Lignin and Lignin-Derived β-O-4 Ether to Cyclohexanols over a CeO2-Doped Carbon-Supported Nickel-Based Catalyst

Catalytic Conversion of Lignin and Lignin-Derived β-O-4 Ether to Cyclohexanols over a CeO2-Doped Carbon-Supported Nickel-Based Catalyst

Selective Production of 4-Propylphenol from Lignin Oil without Exogenous Hydrogen over a RuNi/NiAl2O4 Catalyst

Selective Cleavage of Cβ−O−4 Bond for Lignin Depolymerization via Paired‐Electrolysis in an Undivided Cell

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Catalytic Conversion of Lignin and Lignin-Derived β-O-4 Ether to Cyclohexanols over a CeO₂-Doped Carbon-Supported Nickel-Based Catalyst

Catalytic Conversion of Lignin and Lignin-Derived β-O-4 Ether to Cyclohexanols over a CeO₂-Doped Carbon-Supported Nickel-Based Catalyst

Selective Production of 4-Propylphenol from Lignin Oil without Exogenous Hydrogen over a RuNi/NiAl₂O₄ Catalyst

Selective Cleavage of C_β−O−4 Bond for Lignin Depolymerization via Paired‐Electrolysis in an Undivided Cell