Molecular Catalysis
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2024
·
IF 3.9
Guili Luan,Guihua Yang,Hongyu Wang,Jiaxuan Li,Haojie Sun,Mengyao Sun,Changfei Shi,Shitao Yu,Ji-Jun Zou,Genkuo Nie
(Alkyl-)cyclohexane diols are of high value as industrial reagents and resources, but current producing methods are still unsustainable. Herein, a new method of producing (alkyl-)cyclohexane diols using lignin derived phenols with yield as high as 91.2 % by selective hydrogenolysis is firstly achieved over Nb 2 O 5 and Ni/MCM-41. The hydrogenolysis is completed by designing two-step reactions compositing of selective crack of C(sp 3 )-O bond and selective hydrogenation of benzene ring of lignin derived phenols to achieve a high selectivity. Nb 2 O 5 demonstrates superior activity and long-life time in C(sp 3 )-O bond cleavage compared to commercial solid acids. The robust catalytic performance was thoroughly analyzed through detailed characterization and attributed to the abundant oxygen vacancies produced, which lead more strong L acids and adsorb the methoxy group in lignin derived phenols and at the same time interact with the acid sites to facilitate the cleavage of the C(sp 3 )-O bond. The consequent selective hydrogenation of benzene ring is completed by Ni/MCM-41 easily. More lignin derived phenols are explored in this reaction with (alkyl-)cyclohexane diols universally synthesized. This work provides a new application of lignin derived phenols to synthesize value-added chemicals and makes contribution to sustainable development by biorefineries.
研究领域:
化学工程
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催化
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可持续化学
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生物化学
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DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Guang-Hui Liu,Wen-Ao Shi,Jun Li,Han Wang,Ai-Min Wang,Yu-Hong Kang,Yong Gao,Ni Bai,Jie Kang,Chen Shi,Xian-Yong Wei
To produce high-density liquid fuels from lignite, a novel Ni-based bifunctional MCM-41/ β composite zeolite (Ni@ M / β ) is reported for the catalytic hydroconversion (CHC) of lignite-derived aryl ethers to high-yield polycyclic alkanes (PCAs). Ni@ M / β has a three-dimensional channel-type hierarchical porous texture with β as the core and MCM-41 as the shell. Stable Brønsted/Lewis acid sites and abundant internal/inter-zeolite defects also effectively promote the CHC of aryl ethers to PCAs. Under optimal conditions (5 MPa initial H 2 pressure and 160 °C), selectivities of 2-(benzyloxy)naphthalene (BON) and benzyloxybenzene derived PCAs are as high as 76.0 and 90.5 %, respectively, with dimers and trimers dominating. DFT calculation based on electrostatic potential distribution on the van der Waals surface and Mulliken charge distribution of BON and derived oxygenated monomers shows that aromatic intermediates with >C aromatic OH have multiple accessible sites and are easy to bind with cation/radical fragments. Therefore, it is speculated that PCAs are mainly derived from C-C coupling induced by cation/radical fragments after the activation of aromatic α -carbon. In addition, the activation of H 2 to H + , H · , δ+ H ··· H δ- , and H ··· H is mainly attributed to the strong Ni- M / β interaction and abundant defects. The whole CHC process is triggered mainly by the adsorption of H + released by Ni@ M / β at O sites of aryl ethers, and >C aliphatic -O- bridged bond cleavage is dominant. During this period, benzyl cation/radical produced by >C-O- bond cleavage and aromatic α -carbon activation (mainly) is coupled/reformed with adjacent aromatic fragments into corresponding polymers with non-oxygen bridged bonds, which are more easily converted to PCAs. This polycrystalline composite strategy improves the accessibility of large-sized molecules to active centers, and then increases the yields of PCAs, which is attractive for the clean and efficient conversion of lignite-derived oils to high-density liquid fuels.
研究领域:
化学工程
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能源科学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
·
IF 13.3
Ying Xu,Genkuo Nie,Xiao Jiang,Hongyu Wang,Guihua Yang,Ziyi Yan,Ji-Jun Zou,Hailong Yu,Shitao Yu,Yu Liu
Metal-metal oxide catalysts are robust in selective hydrodeoxygenation of biomass derives. Herein, 1-hexanol in total yield about 76 % is firstly achieved by high selective hydrodeoxygenation of 5-hydroxymethylfurfural over Ni/MCM-41 and Pt-WO X /t-ZrO 2 . By controlling the amount ratio of Ni/Ni 2+ to 0.46, a 99.9 % yield of 2,5-tetrahydrofurandimethanol was achieved from 5-hydroxymethylfurfural by Ni/MCM-41. Subsequently high yield of 76 % of 1-hexanol was obtained by competing pathways of tandem reactions beginning at SN2 reaction at the epoxy atom of 2,5-tetrahydrofurandimethanol to enol/tautomer intermediates and ending with controllable selective hydrogenation. The reaction mechanism is explored and the reaction-oriented regulation is realized by the additional strong BrÖnsted acid sites generated by electron transfer from W to Pt and the appropriate amount of Pt 0 sites of Pt-WO X /t-ZrO 2 , where the ratios of W 5+ /W 6+ and Pt 0 /Pt 2+ are 0.31 and 4.58 respectively. This work provides a new and green method for the synthesis of 1-hexanol and expands the utilization of metal–metal oxide in making value-added products using sustainable feedstocks.
研究领域:
催化
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化学工程
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绿色化学
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生物质转化
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DOI
高影响因子
Science of Advanced Materials
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2020
·Vol. 12
·期 2
·304-311
·
IF 1.117
Xu Gaofeng,Jia Chengxinzhuo,Shi Zhengjun,Liang Ruijuan,Wu Chunhua,Liu Hu,Yan Chao,Fan Jincheng,Hou Hua,Ding Tao,Guo Zhanhu
The ex-situ catalytic cracking of camelina oil using nickel loaded MCM-41 as catalyst at 450 °C in fixed bed reactor was studied. Results revealed that the yield, selectivity and chemical composition of the liquid products was improved by nickel loaded MCM-41 without affecting
the crystalline structure of MCM-41. Moreover, the loaded nickel onto MCM-41 facilitated the cyclization, alkylation, aromatization, deoxygenation, isomerization and cracking reactions.
研究领域:
化学工程
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能源科学
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DOI
高影响因子
ChemCatChem
·
2026
·Vol. 18
·期 2
·e01717
·
IF 3.9
Yimeng Li,Shiji Guo,Ruchao Yin,Jinlong Huang,Ying Kan,Yufei Lan,Hong Zhang,Hailian Tang,Guoyi Bai
The hydrogenation of dioctyl phthalate (DOP) to dioctyl 1,2-cyclohexanedicarboxylate represents an effective pathway for the production of environmentally friendly plasticizers. However, due to the intrinsic stability of the aromatic ring, the development of efficient and stable non-noble metal catalysts remains a key challenge. In this work, an efficient and stable La-modified MCM-41-supported Ni catalyst (Ni/La-M) was developed. The effects of different La introduction methods on the structural and catalytic properties of the catalyst were systematically investigated. The Ni/La-M catalyst, prepared via a two-step hydrothermal method, achieved 99% DOP conversion under mild conditions (140 °C, 2 MPa H 2 , 1 h) and retained over 90% activity after nine cycles. Characterization results revealed that La incorporation significantly enhanced the interaction between Ni and the support, effectively suppressed Ni particle sintering, and increased the fraction of exposed active sites. Compared with other La-introduction methods, the “La-first, Ni-second” strategy exhibited superior activity retention and cycling stability. This approach provides a new design strategy concept for constructing high-performance non-noble metal catalysts in a controllable manner. Graphical La was introduced during MCM-41 synthesis to build a La-modified support, enhancing Ni–support interaction, dispersing Ni species, and increasing catalyst acidity. This strategy improves catalytic activity for dioctyl phthalate hydrogenation to dioctyl 1,2-cyclohexanedicarboxylate and suppresses Ni sintering and leaching, providing mechanistic insight for designing stable green hydrogenation catalysts.
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DOI
高影响因子
Catalysts
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2016
·Vol. 6
·期 9
·134
·
IF 2.964
Songbai Qiu,Ying Xu,Yujing Weng,Longlong Ma,Tiejun Wang
A series of MCM-41 supported Ni catalysts with high metal dispersion was successfully synthesized by simple co-impregnation using proper ethylene glycol (EG). The acquired Ni-based catalysts performed the outstanding hydrogenolysis activity of guaiacol. The effects of the synthesis parameters including drying temperature, calcination temperature, and metal loading on the physical properties of NiO nanoparticles were investigated through the use of X-ray diffraction (XRD). The drying temperature was found to significantly influence the particle sizes of NiO supported on MCM-41, but the calcination temperature and metal loading had less influence. Interestingly, the small particle size (≤3.3 nm) and the high dispersion of NiO particles were also obtained for co-impregnation on the mixed support (MCM-41:HZSM-5 = 1:1), similar to that on the single MCM-41 support, leading to excellent hydrogenation activity at low temperature. The guaiacol conversion could reach 97.9% at 150 °C, and the catalytic activity was comparative with that of noble metal catalysts. The hydrodeoxygenation (HDO) performance was also promoted by the introduction of acidic HZSM-5 zeolite and an 84.1% yield of cyclohexane at 240 °C was achieved. These findings demonstrate potential applications for the future in promoting and improving industrial catalyst performance.
研究领域:
催化化学
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能源化学
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材料化学
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工业催化
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生物质转化
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DOI
高影响因子
CATALYSIS COMMUNICATIONS
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2013
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IF 2.915
Songbai Qiu,Xue Zhang,Qiying Liu,Tiejun Wang,Qi Zhang,Longlong Ma
A simple method for preparing highly active and dispersed supported metal catalysts was developed by co-impregnation. Compared with conventional wetness impregnation, addition of moderate ethylene glycol into the metal nitrate aqueous solution could enhance interaction with MCM-41 surface, resulting in formation of very small NiO particle size (3.5 nm) and high dispersion of the active phase. The Ni/MCM-41 catalysts using co-impregnation exhibited excellent catalytic performance for low temperature hydrogenation of naphthalene with 100% conversion at 55 °C, which could rival the activity of commercial Raney Ni catalyst. The obtained catalysts were characterized by XRD, TEM, TG-DSC, FT-IR, BET and TPR.
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DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Wenlong Gao,Jinpeng Wei,Yonggang Sun,Yuyu Wang,Feng Lin,Yulong Ma
A composite catalyst that combines acid and metal catalysis has been developed. • Selectivity of up to 83.12 % toward MAHs achieved in lignin pyrolysis. • Heating rate affects routes and activation energy in catalytic lignin conversion. • SiW affords B acid sites while Ni centers stabilize intermediates and inhibit coking. To address the challenges of complex deoxygenation pathways and low monoaromatic hydrocarbon (MAHs) selectivity in the catalytic conversion of lignin, a series of SiW/Ni-MCM-41 metal–acid bifunctional catalysts were synthesized via an incipient wetness impregnation method. The effects of silicotungstic acid (SiW) loading ratios on the physicochemical properties of the catalysts and their performance in lignin catalytic pyrolysis were systematically investigated. Characterization results revealed that both SiW and Ni species were highly dispersed on the surface of the MCM-41 support, with interactions between them. With increasing SiW loading, specific surface area and pore volume decreased, Brønsted acid proportion increased, and total acid sites decreased mainly due to Lewis acid loss, enabling Brønsted/Lewis acid balance tuning. Catalytic performance evaluation demonstrated that the catalyst with a SiW-to-Ni-MCM-41 mass ratio of 1:2 exhibited the optimal lignin conversion (80.25 %) and MAHs selectivity (83.12 %), alongside excellent universality in substrate extension experiments. Kinetic analysis indicated that the apparent activation energy is heating-program dependent. In-situ FTIR confirmed that the Brønsted acid sites provided by SiW promoted deoxygenation and alkylation reactions, the Ni metal centers assisted deoxygenation and stabilized the aromatic ring structure via hydrogen-transfer-related pathways, while inhibiting condensation and coking side reactions to a certain extent; and the mesoporous MCM-41 framework provided a highly dispersed environment and a possible confinement-like effect, collectively driving the efficient conversion of lignin into monoaromatic hydrocarbons. This study provides a novel design strategy for metal–acid synergistic catalysts in the field of high-value conversion of lignin. Download: Download high-res image (144KB) Download: Download full-size image
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DOI
高影响因子
FUEL
·
2020
·
IF 5.578
Ze Zhang,Jun Cheng,Yanxia Zhu,Hao Guo,Weijuan Yang
To promote hydrocracking and isomerization activities of bifunctional catalyst for the conversion of methyl palmitate into jet biofuel, phosphotungstic acid (HPW) loaded on Ni/MCM-41 catalyst enhanced strong acidity to strengthen conversion pathways of hydrocracking and isomerization. In the bifunctional catalytic system, Ni catalyzed hydrodeoxygenation and dehydrogenation of methyl palmitate to produce 1-pentadecene, while acid sites catalyzed further conversion of 1-pentadecene to produce jet fuel range hydrocarbons. Quantum chemistry calculation showed that activation energy in chemisorption process of 1-pentadecene onto acid sites significantly reduced from 203.9 kJ/mol with MCM-41 to 81.6 kJ/mol with HPW. Since bond order of β-scission site in 1-pentadecene over HPW was 0.93% lower than that over MCM-41, and Hirshfeld atomic charge of carbenium ion in 1-pentadecene over HPW (0.0722) was much higher than that over MCM-41 (0.0473), HPW showed better catalytic activities than MCM-41 in both hydrocracking and isomerization processes. The overall selectivity of jet biofuel increased to 86.1% with 47.1% n-alkane selectivity and 8.3% iso-alkane selectivity, due to improved strong acid density from 0.563 to 0.730 mmol/g over 20% HPW-Ni/MCM-41 catalyst.
研究领域:
催化化学
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能源科学
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材料科学
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产品关联
DOI
高影响因子
CANADIAN JOURNAL OF CHEMICAL ENGINEERING
·
2025
·
IF 1.9
Sarmad Soomro,Zhenkun Sun,Dennis Y. Lu,Zhihao Zhou,Lin Li,Lunbo Duan
Catalyst deactivation due to carbon deposition and sintering poses a significant challenge to the efficient dry reforming of CH 4 and CO 2 into syngas, particularly at high Ni loadings. To tackle this difficulty, ordered mesoporous silicas with varied pore symmetries were employed as supports in this study to synthesize the Ni-based catalysts using hydrothermal treatment. The 10% Ni/MCM-41 catalyst exhibited the highest conversion rates for CO 2 (81%) and CH 4 (77%), with favourable H 2 /CO (0.92) ratios indicating efficient syngas production Higher Ni concentrations increase active sites and catalytic performance, they also increase carbon deposition, reducing catalyst durability. At lower Ni loadings (4% Ni), catalysts with a 3D pore structure showed improved activity and stability, effectively reducing carbon deposition. This study demonstrates that optimized mesopore symmetries and Ni loadings can enhance catalyst efficiency and durability for syngas production.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）