Catalysts
·
2022
·Vol. 12
·期 12
·1625
·
IF 4.501
Bo Chen,Zhi-Ze Cao,Zhi-Jun Diao,Liang-Qiu Huang,Si-Jia Zhao,Hong Yuan,Jia-Meng He
Hydrogenolysis via targeted depolymerization of C–O linkages is a techno-economic beneficial process for converting lignin into highly valuable chemicals and clean fuels. In this work, a macroporous silicalite-1 (S-1) array-supported Ru-Ni metallic phosphide composite (Ru-Ni12P5/S-15) was prepared as a catalyst and hydrogenolysis activity under relative mild conditions was investigated using a series of compounds containing ether linkages as lignin-related model compounds. The Lewis acid sites originating from the unreduced Ru species and the macroporous geometry of S-1 significantly influenced hydrogenolysis activity and product selectivity. Analysis of the mechanism demonstrated that both the aryl ether and aliphatic ether linkages were directly hydrogenated over Ru-Ni12P5/S-15. 2D-HSQC-NMR spectroscopy demonstrated that the ether linkages of lignin were efficiently cleaved by Ru-Ni12P5/S-15. Furthermore, the obtained liquid hydrogenolysis products are high value-added chemicals used for pharmaceutical production and can be facilely tuned via the reaction conditions.
研究领域:
催化化学
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可再生资源转化
✓ 已验证
DOI
高影响因子
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.
研究领域:
化学工程
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可再生资源转化
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2022
·Vol. 12
·期 10
·1278
·
IF 4.501
Ying Wang,Huilin Xie,Kunming Liu,Jinhui Li,Jin-Biao Liu
Herein, we report a copper-catalyzed C-O cross-coupling of N-methoxy amides and arylboronic acids for the synthesis of aryl-N-methoxy arylimides. The fully selective O-arylation of the N-methoxy amides is found to be greatly prompted by the inexpensive and commercially available CuI. The reaction conditions tolerate a variety of functional groups and promote different reactivities depending on the electronic and steric properties of the distorted substrates.Keywords:copper catalyzed;N-methoxy amides;selective C-O cross-coupling;aryl-N-methoxy arylimides
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
高影响因子
ACS Applied Polymer Materials
·
2022
·
IF 4.855
Yue Yao,Baolong Wang,Feng Zhao,Zhen Hu,Yudong Huang
The extensive use of unsaturated polyester resins and their composites has resulted in an increasingly aggravating problem of waste materials which are difficult to remold or degrade endowed by their highly crosslinked network. A simple and facile recovery method to fully degrade resins remains challenging so far. Here, a hindered C–O bond with a carbonyl group in the β-position of steric ester was introduced into the design and preparation of a dimethacrylate monomer and its self-polymerized unsaturated polyester resin. The obtained resin with good thermal, mechanical, and solvent-resistance properties could be efficiently degraded within 3.5 h at 90 °C at an 80% concentration of aqueous hydrazine hydrate. Selective cleavage of the hindered bond due to steric and electronic effects was activated by the prior addition of the introduced carbonyl group. Degradation products rich in benzene and carboxyl/carboxylate groups respectively could be separated readily according to the water solubility, being expected to be reused as a flocculant and other functional additives. This work provides a promising strategy for the facile recycling of unsaturated polyester resins.
研究领域:
材料科学
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化学工程
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环境科学
✓ 已验证
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2025
·
IF 11.3
Hong Meng,Junhui Zhou,Chunyang Nie,Wenhao Li,Didi Li,Yongqing Zhang,Zhimin Ao
Understanding the metal bonding types in biochar and their effects on peroxymonosulfate (PMS) activation is essential for selecting appropriate biomass and developing efficient catalysts. This study reports a dual-pathway non-radical oxidation system activated by Mn-doped biochar (P-Mn-TPs-900). In the P-Mn-TPs-900/PMS system, phenol degradation reached 100 % within 60 min across a broad pH range (5 −10). Additionally, this oxidation system exhibited excellent stability (5 cycles), maintaining at least 74 % degradation efficiency in the presence of background ions or humic acid. Experimental results and density functional theory (DFT) calculations identified: i) C-O-Mn sites as the primary active sites for PMS activation, facilitating the formation of singlet oxygen ( 1 O 2 ) which was the key reactive oxygen species for phenol degradation; ii) phenol adsorbed on the P-Mn-TPs-900 surface was degraded via an electron transfer process between sulfate groups and phenol. DFT calculations showed strong hybridization between the Mn 3d-orbital, the O 2p-orbital, and the corresponding 2p-orbitals of carbon, which enhanced biochar's catalytic capability. This study provides insights into the role of the C-O-Mn site in PMS activation and offers guidance for selecting suitable biomass for developing practical Fenton-like systems in wastewater treatment.
研究领域:
环境科学
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催化化学
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废水处理
✓ 已验证
产品关联
DOI
PubMed
高影响因子
GREEN CHEMISTRY
·
2015
·Vol. 17
·期 5
·3010-3017
·
IF 8.02
Yao-Bing Huang,Long Yan,Meng-Yuan Chen,Qing-Xiang Guo,Yao Fu
Direct hydrogenolysis of the aromatic Csp2–O bonds in both phenols and phenyl ethers to form arenes selectively is a core enabling technology that can expand greatly the scope of chemical manufacture from biomass. However, conventional hydrogenolysis of phenols typically led to aromatic ring saturation instead of the cleavage of the Csp2–O bonds. Herein, we report a recyclable Ru–WOx bifunctional catalyst that showed high catalytic activities for the hydrogenolysis of a wide range of phenols and phenyl ethers, including dimeric lignin model compounds and the primitive phenols separated from pyrolysis lignin, to form arenes selectively in water. Preliminary mechanistic studies supported that the reactions occurred via a direct cleavage of the Csp2–O bonds and the concerted effects of the hydrogenating Ru sites and the Lewis acidic W sites are the key to such an unusual reactivity.
研究领域:
催化化学
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可再生资源化学
✓ 已验证
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Jia-Pei Guo,Fang-Jing Liu,Lei-Lei Bie,Xing-Gang Si,Yan-Hong Li,Ping Song,Nian Liu,Yun-Peng Zhao,Zai-Xing Huang,Jing-Pei Cao,Xian-Yong Wei
The utilization of lignin to produce high value-added chemicals is conducive to alleviating the fossil energy crisis. Herein, Ni nanoparticles supported on iron/nitrogen co-doped carbon was prepared by co-pyrolysis and solvothermal reduction method for catalytic hydrogenolysis (CH) of dealkaline lignin and its model compounds. The catalysts were prepared under different calcination temperature, N/C ratio and Ni loading, and the optimal catalyst was Ni 10% @Fe/NC 0.33 – 800 (calcination temperature: 800 °C, N/C ratio: 0.33, Ni loading: 10%) based the on the CH of benzyl phenyl ether (BPE). Ni 10% @Fe/NC 0.33 – 800 showed good catalytic performance on the selective cleavage of C-O bond of lignin and its model compounds. The BPE conversion reached up to 97.7% over Ni 10% @Fe/NC 0.33 – 800 under mild conditions (230 °C, 1 MPa H 2 , and 0.5 h) with toluene and cyclohexanol as major products. Catalyst characterizations suggest that N content affects the formation of NiFe alloy and the synergistic effect between Ni and Fe plays an important role in CH of BPE. Moreover, Ni 10% @Fe/NC 0.33 – 800 could promote the cleavage of C-O bonds in dealkaline lignin through CH and hence enhance producing aromatics such as phenols, aromatic ethers, and aromatic esters, among which phenols are the main aromatics with guaiacols predominant.
研究领域:
化学工程
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材料科学
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可再生资源利用
✓ 已验证
产品关联
DOI
高影响因子
Science Advances
·
2020
·Vol. 6
·期 45
·
IF 13.117
Jiang Yan,Qinglei Meng,Xiaojun Shen,Bingfeng Chen,Yang Sun,Junfeng Xiang,Huizhen Liu,Buxing Han
Phenol is an important commodity chemical in the industry, which is currently produced using fossil feedstocks. Here, we report a strategy to produce phenol from lignin by directly deconstructing C sp2 –C sp3 and C–O bonds under mild conditions. It was found that zeolite catalyst could efficiently catalyze both the direct C sp2 –C sp3 bond breakage to remove propyl structure and aliphatic β carbon–oxygen (C β– O) bond hydrolysis to form OH group on the aromatic ring. The yield of phenol could reach 10.9 weight % with a selectivity of 91.8%. In this unique route, water was the only reactant besides lignin. A scale-up experiment showed that 4.1 g of pure phenol could be obtained from 50.0 g of lignin. The reaction pathway was proposed by a combination of control experiments and density functional theory studies. This work opens the way for producing phenol from lignin by direct transformation of C sp2 –C sp3 and C–O bonds in lignin.
研究领域:
催化
·
绿色化学
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生物质转化
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化学工程
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有机化学
✓ 已验证
DOI
高影响因子
Nano Research
·
2023
·
IF 9.9
Liu Guangyong,Lu Yumiao,Lu JunFeng,Wang Yanlei,Liang Shijing,He Hongyan,Jiang Lilong
Electrocatalytic depolymerization of lignin into value-added chemicals offers a promising technique to make biorefining sustainable. Herein, we report a robust trimetallic PdNiBi electrocatalyst for reductive C-O bond cleavage of different lignin model dimers and oxidized lignin under mild conditions. The reduction reaction proceeds with complete substrate conversion and excellent yields toward monomers of phenols (80%–99%) and acetophenones (75%–96%) in the presence of an ionic liquid electrolyte with operational stability. Systematic experimental investigations together with density functional theory (DFT) calculations reveal that the outstanding performance of the catalyst results from the synergistic effect of the metal elements, which facilitates the easier formation of a key C α radical intermediate and the facile desorption of the as-formed products at the electrode. The results open up new opportunities for lignin valorization through the green electrocatalytic approach.
研究领域:
化学工程
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可再生能源
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2013
·
IF 1.304
Qi SONG,Jiaying CAI,Junjie ZHANG,Weiqiang YU,Feng WANG,Jie XU
Phenethyl phenyl ether (PPE) was selected as a typical lignin model compound and hydrogenated and cleaved over two readily accessible nickel-based catalysts, which could be easily separated from the product mixture. The results revealed that the reduction of the nickel catalyst with gaseous hydrogen produced a species capable of achieving higher activity towards C-O-C bond cleavage compared to the Ru/C and Pd/C catalysts. The selectivity of the C-O-C bond cleavage over the Ni/C catalyst was 85%, and higher than the corresponding values in the Ru/C (40%) and Pd/C (69%) systems. Using the carbothermal reduction method for the production of the Ni/C-C catalyst, the conversion and selectivity levels reached 99%, with 40% of the benzene rings in PPE being reserved. In comparison, no benzene ring containing products wer observed over the noble metal catalysts. This difference was attributed to the interaction between the carbon support and the nickel nanoparticles. 摘要 研究了Ni基催化剂上木质素模型化合物苯基苯乙醚中C–O–C键加氢裂解性能. 结果表明, 14;Ni/C催化剂显示出优异的加氢裂解能力, 14;苯基苯乙醚的转化率达到99%以上. Ni/C催化剂的还原方法对裂解选择性有重要影响; 氢气还原制备的Ni/C-H催化剂上, 14;C–O–C键裂解选择性为85%. Ru/C和Pd/C催化剂上裂解选择性分别为40%和69%. 采用碳热还原方法制备的Ni/C-C催化剂, 14;可以实现高选择性加氢和裂解, 14;C–O–C键裂解选择性达到99%以上, 14;其中芳烃化合物收率为44%. 这可能与镍组分和载体碳之间的相互作用有关.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF THE ENERGY INSTITUTE
·
2023
·
IF 5.7
Han-Bing Gao,Yun-Peng Zhao,Bing-Hu Xie,Le-Le Qiu,Jian Xiao,Jing Liang,Jian Li,Fang-Jing Liu,Yue-Lun Wang,Jing-Pei Cao
Selective hydrogenolysis of C–O bonds in lignin is regarded as an important process to produce high value-added chemicals and biofuels. Herein, high-performance Ru-based catalysts (Ru/AC) supported on activated carbon (AC) derived from corncob waste were prepared by a simple impregnation method. The optimal 5%Ru/AC possessed enormous specific surface area, well-developed porosity, high metal dispersion, small Ru particle size and strong metal-support interaction, showing a marvelous catalytic performance in the hydrogenolysis of diphenyl ether, benzyl phenyl ether and phenylethyl phenyl ether with different kinds of C–O bonds under mild conditions. Besides, various phenolic compounds were selectively hydrogenated into cycloalkanols and cycloalkanes over 5%Ru/AC, indicating the excellent catalytic activity in aromatic ring hydrogenation of this catalyst. In addition, high conversion of diphenyl ether and high selectivity of monomeric products were well maintained after employing this catalyst at least three times. The construction and application of the ingenious 5%Ru/AC catalyst highlighted a promising approach to the value-added utilization of lignin-derived aromatic compounds.
研究领域:
催化化学
·
可再生能源
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Yafei Li,Boyang Liu,Yu Wang,Shiqing Wang,Xiaocheng Lan,Tiefeng Wang
It is important but challenging to develop non-noble metal catalysts with high activity and selectivity for biomass conversion. The activation of C═O bond is a crucial step in biomass upgradation. Herein, a series of Ni-xP/Al2O3 catalysts with different P/Ni molar ratios were prepared for the conversion of ethyl levulinate to γ-valerolactone. The developed Ni-0.38P/Al2O3 catalyst was 5.4 times more active than conventional Ni/Al2O3 based on turnover frequency and significantly outperformed the state-of-the-art non-noble metal catalysts. The unique catalytic performance was ascribed to the formation of Ni3P phase, which was identified by several characterizations. The results of DFT calculation and characterization by XPS and CO-FTIR revealed that electron was transferred from Ni to P with the formation of Niδ+ sites. In situ FTIR for the surface reaction indicated that Niδ+ acted as a new active site to activate the C═O bond, which rendered the high intrinsic activity of Ni3P for the C═O hydrogenation of EL.
研究领域:
催化
·
化学工程
·
材料科学
·
生物质能源
✓ 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）