Applied Catalysis O: Open
·
2024
·
IF 0
Kaiyang Xu,Lingfeng Weng,Lizhi Wu,Li Tan,Yu Tang
Cyclohexanone is a key raw material for manufacturing nylon and other chemicals. The sustainable conversion of biomass-derived phenol to cyclohexanone meets the requirements of sustainable development goal but still be challenging. Herein, a catalyst containing isolated Pd cations in zeolite, namely Pd 1 /ZSM-5, is investigated for the partial hydrogenation of phenol to cyclohexanone. Under 140 °C and 1.5 MPa of initial hydrogen pressure, the conversion of phenol reaches 95.6% with the selectivity to cyclohexanone of 99.9%. Besides, the turnover rate (TOR) of partial hydrogenation of phenol reaches 382.7 h −1 . The mild adsorption affinity of cyclohexanone on catalytic sites leads to the high selectivity. Moreover, as unveiled by surface reactivity of phenol monitored by in-situ infrared spectrum, the oxygen atom of phenol hydroxyl group is adsorbed on the Brönsted acid site of Pd 1 /ZSM-5 as the key reaction step. The reaction intermediate involves the partial hydrogenation of benzene ring of phenol.
研究领域:
催化化学
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绿色化学
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可持续发展
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生物质转化
✓ 已验证
DOI
JOURNAL OF MATERIALS SCIENCE
·
2020
·Vol. 55
·期 24
·10482-10491
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IF 3.553
She Tiantian,Niu Libo,Nie Shilin,Li Huafan,Qiao Xianliang,Ma Yuanyuan,Han Xue,Chen Guofeng,Bai Guoyi
A novel sodium alginate-based Pd-3D double network hydrogel Pd/Ca–Alg–PAAS has been fabricated and successfully applied in the selective hydrogenation of phenol for the first time. The prepared catalyst showed excellent catalytic activity and high selectivity (99.8%) for cyclohexanone in the selective hydrogenation of phenol. Furthermore, this double network hydrogel of Pd/Ca–Alg–PAAS still kept a conversion of over 80% with the selectivity for cyclohexanone being over 99% after 6 runs, superior to the single network hydrogel of Pd/Ca–Alg. TEM and FT-IR results demonstrated that the Pd species were highly dispersed in Pd/Ca–Alg–PAAS, and the addition of sodium polyacrylate could enhance the interaction between hydrogel and Pd 2+ and thus inhibit the agglomeration and loss of the active Pd species, accounting for the good stability of Pd/Ca–Alg–PAAS.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2022
·Vol. 46
·期 48
·23312-23320
·
IF 3.925
Zegang Qiu,Zongxuan Li,Shaobo Ma,Zhiqin Li,Yueling Cao,Guangyu Li
The development of a highly effective non-noble metal catalyst for the synthesis of cyclohexanols with high selectivity is very important for the value-added utilization of lignin-derived phenolic compounds. In this paper, a promising Co/NPCN (nitrogen-doped porous carbon nanotubes) catalyst with Co nanoparticles (NPs) embedded in nitrogen-doped carbon for selective hydrogenating of phenol was prepared by introducing an appropriate amount of g-C3N4 (graphitic carbon nitride) into the preparation of ZIF-67 (Zeolite imidazolate framework). Characterization results reveal that the introduction of g-C3N4 of an appropriate amount reduces the size of Co NPs, improves the specific surface area and pore volume, and facilitates the formation of Co0. Full phenol conversion with 100% cyclohexanol selectivity could be achieved at 120 °C, 3 h and 2 MPa H2 over Co/NPCN. In addition, Co/NPCN presents great stability and scalability of the substrate in the phenol hydrogenation reaction. The DFT (density functional theory) calculations reveal that the parallel adsorption configuration of phenol is preferential, which favors the hydrogenation of phenol to cyclohexanol with high selectivity.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
DIAMOND AND RELATED MATERIALS
·
2020
·
IF 2.65
Yanxi Qin,Rongyu Li,Wei Mi,Wei Shi,Baoying Lu,Xili Tong
Aqueous catalytic phenol has been explored using Pd 7 P 3 /SiC catalysts in the presence of H 2 . Palladium phosphide was prepared by oleoamine reduction and supported on silicon carbide. The physicochemical properties of the catalyst were characterized by inductively Coupled Plasma Emission Spectrometer (ICP-MS), X-ray diffractometer (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results show that palladium phosphide is successfully supported on silicon carbide, and the dispersion is relatively uniform with the particle size is about 6–9 nm. Under the same catalytic conditions, a catalyst with a loading of 2.4 wt% exhibits the best activity. When the temperature is 40 °C, the initial pressure is 5 bar, the conversion of phenol can reach more than 99%, and the selectivity of cyclohexanol reaches 94% after 2 h reaction.
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2019
·
IF 5.155
Jiuxuan Zhang,Hong Jiang,Yefei Liu,Rizhi Chen
ZIF-derived N-doped carbon (CN) materials were modified in this work by TiO 2 nano-islands with oxygen vacancies (O V ) through a sol-gel method and subsequent thermal treatment. By loading Pd nanoparticles (NPs) on CN@TiO 2 , Pd@CN@TiO 2 catalysts were fabricated. Superior catalytic performance of Pd@CN@TiO 2 was found in the selective phenol hydrogenation to cyclohexanone , with a TOF of 30.1 h −1 , 2.2-fold as high as that of Pd@CN. The synergistic effect of CN and TiO 2 nano-islands was responsible for the superior catalytic performance. More O V was generated due to the high specific surface area of CN. At the same time, CN could also enhance the hydrophilicity , and adsorb more phenol in non-planar fashion. The TiO 2 nano-islands with O V could improve the Pd dispersion, make more Pd element on the support surface, strengthen the antioxidizability of Pd and induce electron-rich Pd NPs. Furthermore, the as-fabricated Pd@CN@TiO 2 showed good recyclability in the phenol hydrogenation, and also exhibited excellent catalytic performance in the catalytic hydrogenation of phenol with diverse functional groups. These findings provide the feasibility of using the high-performance catalysts for the hydrogenation of phenol derivatives.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Huafan Li,Tiantian She,Guofeng Chen,Menghua Sun,Libo Niu,Guoyi Bai
In this paper, a stable Pd/NH 2 -SBA-15 catalyst was prepared by an ammonia evaporation method using amino-functionalized SBA-15 as support. Pd/NH 2 -SBA-15 showed excellent catalytic performance in the selective hydrogenation of phenol to produce cyclohexanone. Furthermore, this Pd/NH 2 -SBA-15 catalyst kept the conversion of phenol and selectivity of cyclohexanone both over 90 % even after 10 runs, much better than Pd/SBA-15 and the previously reported Pd-based catalysts, demonstrating the benefit of amine functionalization on the activity of supported Pd nanoparticles. TEM and XPS results indicate that small Pd particles were highly dispersed on the NH 2 -SBA-15 support and a stronger interaction occurred between the active Pd particles and the amine functionalized SBA-15 support, which could effectively inhibit the agglomeration of the active Pd particles during the reaction and then improve the stability of this catalyst.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS LETTERS
·
2023
·Vol. 153
·期 10
·3044-3052
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IF 2.8
Li Kaihui,Xu Junyuan,Zhang Huan,Zhu Lihua
Abstract Cyclohexanone is a crucial intermediate for producing nylon and other industrial products. However, the direct hydrogenation of phenol for synthesizing cyclohexanone easily generates cyclohexanol and thus reduce the yield. In this work, the Pd/WO 3 catalysts with different Pd contents (Pd/WO 3 -1–0.21 wt%, Pd/WO 3 -2–0.69 wt%, Pd/WO 3 -3–2.20 wt%) are prepared via using sodium borohydride liquid phase reduction, which have good catalytic performance for phenol selective hydrogenation. The Pd/WO 3 -2 catalyst can achieve 92.9% conversion, 84.4% selectivity and high TOF (turnover frequency) of 349.1 h −1 under the reaction conditions (120 °C, 2 h, 3.0 MPa H 2 ). The nanostructures of the catalysts are extensively characterized by XRD, XPS, SEM, TEM, HRTEM, STEM and STEM-EDS elemental mapping and line-scanning. It is found that the Pd/WO 3 -2 catalyst has a high Pd dispersion and quite tiny Pd clusters. Alternatively, the stability experiment of Pd/WO 3 -2 indicates that the conversion decreases from 92.9% to 87.5% and the selectivity to cyclohexanone does not change significantly (84%) after it is recycled for five times. Graphic Abstract
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2015
·Vol. 5
·期 4
·2300-2304
·
IF 5.426
Gang Feng,Ping Chen,Hui Lou
Phenol is an important component of pyrolysis bio-oil, especially from lignin, and the conversion of phenol is crucial for the production of biofuel. A cost-effective and efficient catalyst is worth developing in the hydrogenation of phenol. Herein we report that supported palladium nanoparticles on carbon–nitrogen composites with high surface area are highly active for aqueous-phase hydrogenation of phenol. The conversion of phenol was 91.7% within 1 h at 80 °C. Higher activity was achieved at higher temperature. The synergy between palladium nanoparticles and the carbon–nitrogen composite support accelerated the hydrogenation of phenol, which clarified the crucial role played by the support. The hydrogenation of phenol highlights the potential of these catalysts for upgrading bio-oil.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Junyuan Xu,Lihua Zhu,Huan Zhang,Xin Deng,Kaihui Li,Bing Hui Chen
Cyclohexanone is significant chemical reagent for organic synthesis, so it is key to design and prepare a highly active and environmentally friendly catalyst for the conversion of phenol to cyclohexanone . The results in this work show that the Pd-based supported nanocatalysts (Pd/SiO 2 ) with various Pd contents (Pd/SiO 2 –1 with 0.16 wt% Pd, Pd/SiO 2 –2 with 0.26 wt% Pd, Pd/SiO 2 –3 with 0.52 wt% Pd, Pd/SiO 2 –4 with 2.60 wt% Pd) have high conversion and selectivity in phenol selective hydrogenation to cyclohexanone under relatively moderate reaction parameters, Pd/SiO 2 –2 with the highest conversion of 80.6%, selectivity of 92.1% and turnover frequency (TOF) of 1106.1 h −1 . This excellent activity is attributed to the highly dispersed Pd nanoparticles (NPs) on silica with high surface area. The Pd/SiO 2 catalysts are with high Pd dispersion and strong interaction of Pd-SiO 2 , which have been proved by XRD, XPS, BET, TEM, HRTEM, STEM, STEM-EDS elemental analysis techniques. The as-prepared materials have good catalytic behaviors in the selective hydrogenation of phenol and good stability, facilitating phenol hydrogenation to cyclohexanone and preventing the excessive hydrogenation of cyclohexanone to cyclohexanol.
研究领域:
化学工程
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材料科学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Chuanchuan Zhao,Ziyi Zhang,Yaru Liu,Ningzhao Shang,Hai-Jun Wang,Chun Wang,Yongjun Gao
A kind of natural, sustainable, and abundant biomass, chitin, is used as support to load palladium nanoparticles catalyst (Pd–chitin) for the transfer hydrogenation of phenolic compounds to ketones in HCOONa solution. The appropriate reduction temperature in hydrogen atmosphere is a key factor to improve the coordination between oxygen-containing groups and palladium nanoparticle, which prevents palladium nanoparticles leaching during the reaction so that Pd–chitin-150 exhibits good recycling stability. More importantly, Pd–chitin-150 can be fabricated into a PTFE tube with 2 mm inner diameters as a kind of monolithic catalyst, achieving the continuous production of cyclohexanone by feeding the mixture of phenol and HCOONa solution. The functions of sodium introduced during the preparation of catalyst are researched by H2-TPR, CO–DRIFT, and DFT calculations, which facilitate the reduction of palladium and increase the catalytic activity for phenol hydrogenation and selectivity to cyclohexanone.
研究领域:
催化化学
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生物质材料
·
绿色化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2021
·
IF 8.128
Shaodan Xu,Jia Du,Qingwei Zhou,Huanxuan Li,Chunhui Wang,Junhong Tang
Selective hydrogenation of phenol is promising for the utilization of renewable lignocellulose and production of cyclohexanone that usually relies on petroleum, but it is challenging to simultaneously achieve high activity and selectivity. Herein, we report an amino-functionalized nanoporous polymer stabilized palladium nanoparticle catalyst, which is prepared via a one-pot co-polymerization method, as highly active and selective catalysts for the phenol hydrogenation, giving cyclohexanone selectivity over 99.5% with full conversion of phenol under mild reaction conditions without any soluble additives. Importantly, the palladium leaching was efficiently hindered, maintaining the catalytic performances in continuously recycle tests. In contrast, the commercial palladium catalysts exhibit much lower selectivity and obvious deactivation because of the palladium leaching.
研究领域:
催化化学
·
材料科学
·
可再生资源利用
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Fengnan Wang,Jiuxuan Zhang,Yanhua Shao,Hong Jiang,Yefei Liu,Rizhi Chen
Covalent organic frameworks (COFs) have emerged as an excellent support for heterogeneous catalysis due to their regular pore structure and high specific surface area. Herein, a series of porous TpPa-1 with different morphologies and structures were achieved by adjusting the ratio of water to acetic acid in the solvent-thermal process, and Pd@TpPa-1 catalysts were obtained with Pd solution impregnation. Notably, Pd@TpPa-1-100 prepared with 100 wt % water as the catalyst has superior catalytic properties in the phenol hydrogenation to cyclohexanone, and its turnover frequency (TOF) of 33.1 h–1 is about 7 times higher than that of Pd@TpPa-1-0 synthesized with 100 wt % acetic acid as the catalyst. The two-dimensional (2D) nanosheet structures, highly dispersed Pd nanoparticles (NPs) with small particle size, and superhydrophilicity should be responsible for the superior catalytic performance of Pd@TpPa-1-100. Furthermore, Pd@TpPa-1-100 also has better catalytic performance in the hydrogenation of catechol, resorcinol, and hydroquinone than Pd@TpPa-1-0 and exhibits superior catalytic stability. This study provides a new approach for the structural regulation of metal-based COF catalysts.
研究领域:
材料科学
·
催化化学
✓ 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）