Journal of Environmental Chemical Engineering
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2026
·Vol. 14
·期 5
·124698
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IF 7.5
Jing-jing Wu,Jia-yuan Tian,Feng Lin,Yu-long Ma,Yong-gang Sun,Pei Ma,Shuai-lei Li,Xue Zhang,Yi-shu Ma,Xiao-lin Xue
The efficient hydrodeoxygenation (HDO) of lignin oil to produce high-value-added cycloalkanes is a key route for biomass resource utilization. However, developing catalysts with both high catalytic activity and product selectivity remains a crucial challenge in this field. Herein, a strategy integrating crystalline-phase regulation and hydrogen spillover was proposed. Ru was doped into the ZIF-67 precursor via a one-pot method. After controlled calcination and hydrogen reduction, a nitrogen-doped carbon-coated Ru-Co bimetallic catalyst (RuCo@NC) was successfully prepared. Characterization results showed that the introduction of Ru induced the phase transformation of Co from face-centered cubic (FCC) to hexagonal close-packed (HCP) and precisely regulated the electron density distribution of catalytic active sites through Ru to Co electron transfer. H 2 -TPR/TPD confirmed that Ru, as a hydrogen spillover site, significantly enhanced low-temperature reducibility and hydrogen adsorption capacity. DFT calculations indicated that Ru sites dominated the efficient dissociation and activation of H₂ molecules, while Co sites were responsible for the selective adsorption of substrate molecules. The synergistic effect between the two metals greatly improved the HDO activity of the catalyst. The optimized 0.009RuCo@NC-400 catalyst achieved 100% conversion of lignin oil at 240 °C and 2 MPa H₂, with a cycloalkane selectivity of 73.7%. Moreover, the conversions of ten lignin derivatives were all above 97%. This study reveals a synergistic catalytic mechanism of the 0.009RuCo@NC-400 catalyst, integrating crystalline phase structure, electronic effects, and hydrogen spillover, providing theoretical guidance for the design of efficient HDO catalysts.
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2026
·
IF 6.2
Zong-Pin Fu,Yun-Peng Zhao,Yu-Fa Wu,Qi-Jie Zhou,Shu-Ting Hu,Le-Le Qiu,Fang-Jing Liu,Mei Zhong,Jing Liang,Jing-Pei Cao
Mild thermal dissolution is an effective method for the clean, low-carbon conversion of lignite. However, the resulting products still contain numerous oxygen-bridged bonds and heavy molecular compounds, requiring further upgrading to serve as suitable feedstocks for fuels and chemicals. In this study, a supported Cu-Ni bimetallic catalyst was synthesized via a co-precipitation method and applied to the catalytic hydroconversion (CHC) of thermal dissolution portions from Zhaotong lignite (ZT) and lignite-related model compounds (LRMCs). Catalyst characterization revealed that metal particles were uniformly dispersed on the surface of the Cu-Ni/CoOx-CeO 2 catalyst, along with the formation of defect sites. The CoOx-CeO 2 support promoted surface oxygen vacancy formation. Furthermore, the incorporation of Ni altered the local coordination environment of Cu species through multicomponent interactions. The synergy between interfacial oxygen vacancies and Cu-Ni bimetallic sites significantly enhanced catalytic activity. Tests with LRMCs indicated that the Cu-Ni/CoOx-CeO 2 catalyst selectively cleaves C-O ether bonds under mild conditions, exhibiting both high selectivity and strong hydrogenation activity in the CHC of phenolic compounds. The catalyst also effectively promoted the CHC of macromolecular species in the soluble portion from ZT thermal dissolution, thereby converting phenolic compounds into cycloalkanol. These finding provides valuable insights for developing staged conversion routes and achieving value-added utilization of lignite.
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INORGANIC CHEMISTRY COMMUNICATIONS
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2026
·
IF 5.9
Zongsheng Chen,Yanxi Ma,Hui Kang,Ting Liu,Hao Song,Ludan Chen,Yingluo He
The development of highly active catalysts for the catalytic conversion of oxygen-containing aromatics in lignite under mild conditions is of crucial importance for the production of clean liquid fuels. In this study, an in situ nitrogen-doped carbon-coated Ni@C/g-C 3 N 4 catalyst was fabricated. The abundant lone-pair electrons on nitrogen atoms within the g-C 3 N 4 support can coordinate with nickel, facilitating the migration of electrons toward the nickel surface. This electron transfer process favors the formation of Ni δ+ active sites with low electron cloud density, thereby enhancing the hydrogenation catalytic activity of the catalyst. The catalyst exhibited exceptional performance in lignite hydrodeoxygenation (HDO): under conditions of 80 °C, 1.5 MPa H 2 , and a reaction time of 1.5 h, 100% conversion of the lignite model compound benzyl phenyl ether (BOB) was achieved. Furthermore, the catalyst demonstrated remarkable hydrodeoxygenation activity, with high selectivity toward various oxygen-containing model compounds, including methyl nonanoate and 2,6-dimethylphenol. The optimal catalyst was applied to the catalytic conversion of the soluble portion (SP) of Naomaohu coal (NMHC). Results indicated that, compared with the SP, the hydrogenated soluble products from catalytic hydrogenation conversion (SP CHC ) showed a significant increase in the variety and quantity of aromatic and alkane compounds, while the relative contents of phenols, alcohols, esters, and ethers were reduced. These findings fully confirm that the Ni@C/g-C 3 N 4 catalyst can effectively cleave C C and C O bonds during the hydrogenation conversion of the SP, providing theoretical guidance for the conversion of lignite into high-quality clean liquid fuels.
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APPLIED CATALYSIS A-GENERAL
·
2023
·
IF 5.5
Wenqi Zou,Heyu Li,Minghua Liu,Yuancai Lv
In this study, Cu was loaded on the surface of Ni-MOF by impregnation, and significantly improved the catalytic activity on lignin and its derivatives. The characterization showed that the non-noble bimetallic catalyst owned good dispersion, rich acid sites and stable structure was successfully synthesized. The introduced Cu reduced the reduction temperature of Ni, increased the acidity of the catalyst, and thus improved the catalytic performance and product selectivity of the catalyst. Under the mild conditions (120 °C), the conversion percentage of BPE was as high as 89.6 % using isopropyl alcohol as the hydrogen source. When the reaction temperature was 260 °C, the depolymerization percentage of corn cob lignin was 81.12 %, and the yield of phenol monomer could reach 11.46 wt. %. This work may provide an effective strategy for the preparation of efficient bimetallic catalysts for lignin hydrogenolysis .
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FUEL
·
2022
·
IF 8.035
Han-Bing Gao,Le-Le Qiu,Fa-Peng Wu,Jian Xiao,Yun-Peng Zhao,Jing Liang,Yong-Hui Bai,Fang-Jing Liu,Jing-Pei Cao
Catalytic hydrogenolysis of C O bonds in lignin provides a promising route to produce high value-added biofuels and chemicals. However, designing highly active and stable catalysts for this process is still a challenge. Herein, a series of Ni/Al 2 O 3 catalysts were synthesized by calcination and reduction of layered double hydroxide precursors, and their activities were evaluated in the catalytic conversion of lignin-derived compounds. Diphenyl ether was completely converted with a 100% monomeric selectivity (cyclohexane and cyclohexanol) over the optimized Ni/Al 2 O 3 -500 under the optimal conditions of 200 ℃, 0.5 MPa H 2 and 1.5 h, indicating the excellent catalytic activity in the cleavage of C O bonds of the catalyst. The excellent catalytic performances of Ni/Al 2 O 3 -500 were originated from its relatively large specific surface area, well-developed porosity, small crystallite size, high Ni 0 concentration and strong interaction between the active metal and support. The reusability experiments show that Ni/Al 2 O 3 -500 possesses a relatively high stability for six reuses. Moreover, various lignin model compounds can be completely converted to corresponding monomeric products over Ni/Al 2 O 3 -500, indicating the applicability of this ingenious catalyst. The application of the hydrotalcite-derived Ni-based catalysts with high activity and stability provides a promising approach for the efficient hydrogenolysis of lignin derivatives.
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Journal of Materials Chemistry A
·
2023
·Vol. 11
·期 6
·2595-2617
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IF 11.9
Ruijin Li,Danlian Huang,Lei Lei,Sha Chen,Yashi Chen,Guangfu Wang,Li Du,Wei Zhou,Jiaxi Tao,Haojie Chen
Considering the two limitations of the biocompatibility of metal–organic-frameworks (MOFs) and the low utilization of lignin biomass, herein, we review the interaction between lignin macromolecules and MOFs to promote their high-end applications and sustainability. Firstly, lignin and lignin derivatives can coordinate with metal ions to form bio-based MOFs due to their biocompatibility and surface-rich functional groups, which solves the difficulty of applying the original MOFs in biomedicine and other fields. We introduce the structure, coordination process, and advantages of applying bio-based MOFs in detail and discuss the problem that powdered MOFs are easily blocked and difficult to be separated and recovered. Secondly, MOFs can be used as catalysts to facilitate the conversion of lignin to liquid fuels and fine chemicals, thereby alleviating the energy shortage. We discuss the mechanism and products from the redox depolymerization of lignin using MOFs and their derivatives. The opportunities and challenges encountered in bio-based MOFs and selective cleavage of lignin are discussed based on several perspectives. It is hoped that this study can provide good theoretical guidance for the synthesis of bio-based MOFs and the conversion of lignin.
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FUEL
·
2023
·
IF 7.4
Guang-Hui Liu,Yong-Chao Qi,Han Wang,Ai-Min Wang,Yu-Hong Kang,Yong Gao,Ni Bai,Zhan-Ku Li,Xian-Yong Wei
This paper focused on the complementary advantages of density functional theory (DFT) calculation and catalytic reaction regulation. Based on the effective identification of intermediates, the possible catalytic hydroconversion (CHC) pathways of lignite-derived aryl ethers over Ni/mordenite were discussed. Bond dissociation energy (BDE) calculations of >C–O– bonds in different substrates and intermediates show that BDEs of >C ar –O– bonds are generally higher than those of >C al –O– bonds, and there is obvious electron aggregation near O atoms. Mulliken charge distribution analyses of different atomic sites further revealed the possible adsorption sites of active hydrogen, especially H · and H + . Possible cleavage pathways were further speculated by evaluating the stability of different leaving groups. In the early stage of CHC, aromatic ring hydrogenation and >C al –O– bond cleavage dominate, rather than >C ar –O– bond cleavage. Enthalpy change analyses combined with the CHC of real substrates further indicate that lowering temperature is beneficial to the cleavage of >C ar –O– bonds under the premise of inhibiting H ··· H transfer and obtaining H · effectively. Appropriately increasing the support acidity to ensure sufficient H + release is conducive to >C al –O– bond cleavage, especially direct dehydroxylation/dehydration. The analysis of synergetic transfer pathways of active hydrogen during the CHC provides theoretical guidance for the pathway optimization of converting lignite into high-quality clean liquid fuels.
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Molecular Catalysis
·
2023
·
IF 4.6
Zong-Pin Fu,Yun-Peng Zhao,Fa-Peng Wu,Jin-Xuan Xie,Le-Le Qiu,Jian Xiao,Jing Liang,Yong-Hui Bai,Fang-Jing Liu,Jing-Pei Cao
The selective hydrogenolysis of C O bonds is critical for the effective valorization of lignin. Herein, we synthesized a series of highly efficient Ni x Co y Al-T catalysts by a coprecipitation-calcination-reduction method and evaluated their catalytic hydrogenolysis performance towards the C O bonds of lignin-derived aryl ether, using isopropanol as the hydrogen donor source. The results revealed that the Ni 0.5 Co 1.5 Al-600 catalyst displayed superior activity and its catalytic performances were strongly influenced by the Ni/Co molar ratios and calcination temperatures. The enhanced dispersion of metal particles and the electron transfer from Ni to Co in Ni 0.5 Co 1.5 Al-600 catalyst facilitated the cleavage of C O bonds in lignin model compounds. Furthermore, the β-benzyl-H atom in 2-phenoxy-1-phenylethanol (PPE) also contributes to the cleavage of C aliphatic -O bonds. Under optimized reaction conditions (180 ℃, reaction time 2 h), PPE was completely converted over the Ni 0.5 Co 1.5 Al-600 catalyst, and the yield of ethylbenzene and cyclohexanol reached 95.91wt% and 85.73wt%, respectively. These findings demonstrate that the Ni x Co y Al-T catalytic system holds great promise for the production of valuable chemicals from lignin under mild conditions.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Zhongwei Wang,Xiangqian Chen,Yisheng Sun,Dongliang Hua,Shuangxia Yang,Laizhi Sun,Tianjin Li,Lei Chen
Designing highly active and stable catalysts for the selective cleavage of the C-O bond of lignin is important to convert it into high-valued aromatic compounds. Herein, a facile synthetic strategy was developed using melamine as a soft template to prepare a highly active catalyst consisting of highly dispersed Ni nanoparticles on defective N-doped carbon support. The results indicated that the decomposition of melamine during the pyrolysis process induced the nitrogen atoms into aromatic carbon. The introduction of N-doped carbon support acted as anchor points for the Ni nanoparticles, strengthening the metal-support interaction. Approximately 100 conversion of the representative lignin model compounds, including 2-phenylethyl phenyl ether, were converted into their aromatic monomers under mild conditions. The as-prepared catalyst was stable and reusable after five cycles with no apparent signs of deactivation. Moreover, the theoretical calculation revealed that N-doped carbon supported Ni-based catalyst possessed a lower activation energy of C-O bond than only carbon supported Ni-based catalyst for the C-O bond cleavage in hydrogenolysis of lignin and its model compounds.
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FUEL PROCESSING TECHNOLOGY
·
2022
·
IF 8.129
Wang Li,Wen-Ying Li,Xing-Bao Wang,Jie Feng
During direct coal liquefaction , selective C al –O bond cleavage is critical for phenol production. In this study, anisole and benzyl phenyl ether were chosen as the oxygen-containing model compounds. Radical-induced sites of benzyl phenyl ether were investigated using the Fukui function and energy barrier calculation. The promotion routes of the C al –O bond cleavage in anisole and benzyl phenyl ether by radicals were illustrated. The formation of o -benzyl phenol was regarded as a sign of benzyl radical-induced pyrolysis based on the most optimal path. The competitive process between the optimal path and β-bond scission path was analyzed from the rate constant perspective. Radical-induced pyrolysis made remarkable differences in product selectivity for benzyl phenyl ether. Similarly, the cleavage of the C al –C al bond can also be promoted using two methods of radical induction, which is referred to as a radical chain process. In contrast to benzyl phenyl ethers, the induced pyrolysis of the C al –C al bond in bibenzyl is more likely to occur via β-bond scission after the H of CH 2 is abstracted by a radical. The findings of this research would provide a theoretical foundation for comprehending the radical mechanism of direct coal liquefaction.
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Catalysts
·
2022
·Vol. 12
·期 11
·1328
·
IF 4.501
Liang-Qiu Huang,Zhi-Jun Diao,Bo Chen,Qing-Pan Du,Kai-Yang Duan,Si-Jia Zhao
Efficient depolymerization of C–O linkages is essential for converting lignin into fuels and higher value-added chemicals. In this work, CoRuP/SiO2, an amorphous Ru-Co phosphide composite, was fabricated for the efficient hydrogenolysis of ether linkages. The 4–O–5 andα–O–4 linkages containing lignin-related compounds, such as diphenyl ether, benzyl phenyl ether, 3-methyl diphenyl ether, and dibenzyl ether, are selected as representatives of linkages in lignin. Under mild conditions, Ru-containing metallic phosphides have high-performance for the catalytic depolymerization of C–O linkages. Compared with other catalysts, CoRuP/SiO2shows an outstanding selectivity for benzene and excellent efficiency in depolymerizing diphenyl ethers, yielding only a small amount of by-products. Furthermore, the total acidity shows a linear relationship with the hydrogenolysis reactivity in cleaving aromatic ether bonds. The mechanisms for the catalytic hydrogenolysis of 4–O–5 andα–O–4 bonds over CoRuP/SiO2are proposed. Moreover, two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance spectroscopic analysis demonstrates that CoRuP/SiO2could effectively depolymerize C–O bonds of lignin. These dominant hydrogenolysis products from lignin have excellent potential in the production of high value-added drugs or pharmaceutical intermediates. The hydrogenolysis of lignin can be a highly efficient alternative to the existing method of lignin utilization.Keywords:hydrogenolysis;C–O linkages;metallic phosphides;reaction pathway
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Haichuan Zhang,Zede Yi,Shiyu Fu,Changzhi Li,Lucian A. Lucia,Qiying Liu
A rational design of the intrinsic lattice structure of catalysts is vitally important to address catalytic performance. Herein is reported a top-down synthesis for the fabrication of a bifunctional metallic catalyst. First, palladium nanocubes with (100) lattices planes were synthesized through a shape-control strategy; next, the as-synthesized Pd/Co-ZIF was used as a template for in - situ phase reconstruction by a spontaneous phase transformation process in the presence of H 4 SiW under solvothermal conditions. Ultimately, formation of 3D hierarchical flower-like bimetallic nitride nanosheets (SiW 12 @Pd/Co-ZIF-NS) were generated because of this process. The SiW 12 @Pd/Co-ZIF-NS catalyst not only displays excellent catalytic transfer hydrogenolysis for C-O bond cleavage of lignin dimeric substrates, but also maintains superior recycling durability due to an encapsulation phenomenon preventing aggregation. Finally, the resulting nanocomposites exhibit superior activity and good size selectivity toward catalytic transfer hydrogenolysis of the actual lignin substrates to produce a significant amount of low-molecular-weight aromatic compounds .
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