Molecular Catalysis
·
2024
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IF 3.9
Yuhao Yang,Minghui Tan,Hailun Geng,Xiujuan Gao,Yisheng Tan,Qingde Zhang
Oriented designing the microenvironment of catalytic sites is essential for understanding catalytic processes. In this work, EDTA was first grafted in UiO-66 and then chelated Rh to obtain an efficient catalyst for 1-hexene hydroformylation reaction. EDTA not only served as a chelation site for Rh immobilization in UiO-66, but also markedly influenced the structure and properties of Rh/UiO-66. The incorporation of EDTA reduced the micropore content and suppressed the formation of heavy products. Moreover, the grafted EDTA regulated the electronic state of Rh effectively to improve the CO and propene adsorption, thus constructing an appropriate microenvironment for hydroformylation. Therefore, EDTA-modified Rh/U-E catalyst exhibited higher aldehydes yield, TOF and stability than Rh/U without EDTA. The dual role of EDTA in anchoring Rh sites and modulating the microenvironment for hydroformylation provides more prospects for designing customized MOFs-based catalysts.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2024
·
IF 15.7
Zhounan Yu,Leilei Zhang,Yuanlong Tan,Rizheng Jing,Hongchen Cao,Caiyi Lou,Rile Ge,Junhu Wang,Aiqin Wang,Tao Zhang
Rh-P complexes have been widely used as catalysts for hydroformylation reactions. The extremely high price of Rh and its scarce reserves have prompted the exploration of the alternatives. In this study, we reported that Pt/PS-PPh 2 single-atom catalysts promoted by SnCl 2 were highly efficient and selective for the hydroformylation of higher α-alkenes. A broad scope of substrates (i.e., C 6 –C 12 ) were smoothly converted to the corresponding linear aldehydes with high yields under reaction conditions of 90–120 °C and 4–6 MPa syngas . The turnover frequency (TOF) was comparable to homogeneous Pt-Sn catalysts, and the linear/branched ratio reached as high as > 20. In addition, the catalyst could be reused with the extra addition of SnCl 2 . The promotional role of SnCl 2 was elucidated by quasi- in situ X-ray adsorption fine structure, Fourier transform infrared, and Mössbauer spectroscopy . It was discovered that SnCl 2 was transformed into Sn(dioxane)Cl 3 − species coordinated to Pt as a moderately electron-donating ligand, which, together with the phosphine group, stabilized mononuclear Pt (I) species against reduction and aggregation.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
Molecular Catalysis
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2024
·
IF 3.9
Yifei Chen,Xinnan Zhao,Chen Xin,Xiuqin Dong,Hao Gong
This work explored the role of defective sites on the hydroformylation of n-butene through ligand regulation. The investigation examined the effect of modulator properties on defect sites and rhodium loading, and optimized the H 2 BDC/modulator ratio to improve catalyst activity. Atomically dispersed Rh is anchored to these highly dispersed defect sites, effectively preventing aggregation and thereby enhancing hydrogenation ability. Under optimal conditions, the catalyst achieved a conversion of 96.9 %, with an overall aldehyde selectivity of 90 %. DRIFTS analysis provided compelling evidence that Rh(CO) 2 and HRhCO species were formed on 1Rh/MOF-5-HBC, improving CO insertion capability. This study highlights the significance of MOFs as catalyst supports in enhancing performance through defect engineering. The ability of the modulator to induce defect formation was measured by p K a. Meanwhile, it has been discovered that the length differences between the modulator and the MOF organic ligand can have a significant impact on the stability of defective MOFs.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2017
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IF 4.339
Yuqing Wang,Li Yan,Cunyao Li,Miao Jiang,Wenlong Wang,Yunjie Ding
Porous organic copolymer (denoted as CPOL-BP&P) was afforded through the copolymerization of vinyl biphephos and tris (4-vinylphenyl)phosphine monomers under solvothermal conditions, and followed with impregnation method provided a highly efficient Rh/CPOL-BP&P catalyst with high activity (TOF = 11,200 h −1 ) and regioselectivity (the ratio of linear to branched aldehydes, l:b = 62.2) for heterogeneous hydroformylation of 1-butene. High regioselectivity was also obtained in the hydroformylation of butene mixture (2-butene: l:b = 55.8, isomeric mixture of butenes: l:b = 56.0). The Rh/CPOL-BP&P catalysts were thoroughly characterized by means of nitrogen sorption isotherms, in situ FT-IR, XPS, solid-state 31 P MAS NMR, HAADF-STEM, SEM and TEM. The formation of unique coordination bonds with Rh species in the polymer skeleton was determined. Heterogeneous hydroformylation of butenes was effectively realized due to a synergetic effect between PPh 3 moiety and biphephos moiety.
研究领域:
材料化学
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催化化学
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DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
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2015
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IF 3.615
Miao Jiang,Li Yan,Yunjie Ding,Qi Sun,Jia Liu,Hejun Zhu,Ronghe Lin,Fengshou Xiao,Zheng Jiang,Jingyue Liu
The heterogenization of homogeneous catalysts is of critical importance for both fundamental research and practical applications. The key obstacle to industrial applications of heterogenized homogeneous catalysts is the long-term stability of the immobilized molecular complexes. We unambiguously demonstrate in this report that the vinyl-functionalized PPh 3 polymers supported single Rh sites (Rh/POL–PPh 3 ) catalyst provided not only excellent catalytic activity but also ultrahigh stability for fixed-bed olefins hydroformylation , which is one of the most important industrial homogeneous catalytic processes for the synthesis of aldehydes and alcohols. HAADF-STEM and EXAFS results indicated that the Rh atoms were present in single Rh sites which were strongly coordinated with the exposed phosphorous atoms of the POL–PPh 3 support. The Rh/POL-PPh 3 catalyst provided high activity and selectivity because it maintained the catalytic functionalities similar to the homogeneous HRh(CO)(PPh 3 ) 3 complex, as demonstrated both by 31 P MAS NMR and in situ FT-IR experiments. Thus a reaction mechanism, similar to that over the homogeneous HRh(CO)(PPh 3 ) 3 complex, was proposed for olefin hydroformylation over the novel Rh/POL–PPh 3 catalyst.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Xiuqin Dong,Chen Xin,Lingtao Wang,Hao Gong,Yifei Chen
Immobilization of the Rh active sites in novel porous materials has attracted attentions for solving the problems of separation and recycling of homogeneous catalysts. In this work, a comparative study of phosphine modified 1Rh/MOF-5 using three different methods was reported, namely 1Rh-P/MOF-5, 1Rh/MOF-5-P and 1Rh/MOF-5-PPh 3 . Similar with the traditional methods, PPh 3 was etched on Rh particles by impregnation in 1Rh-P/MOF-5 and encapsulated in the pores by solvothermal method in 1Rh/MOF-5-P. Moreover, we proposed a novel post-synthesis strategy for grafting phenyl phosphine on the organic linkers in 1Rh/MOF-5-PPh 3. The position of phenyl phosphine in MOFs and the effect of phosphine on the Rh active sites in hydroformylation were investigated by XRD, IR, XPS, TGA and DRIFTS. 1Rh/MOF-5-PPh 3 exhibited the best catalytic activity and stability than 1Rh-P/MOF-5 and 1Rh/MOF-5-P in the hydroformylation of 1-butene. Different P/Rh ratio in P-modified 1Rh/MOF-5 led to the spatial environment change around the Rh active sites. This study showed details in the role of phosphine ligands played in hydroformylation reactions and provided some guidance for MOFs materials in the immobilization of homogeneous catalysts.
研究领域:
化学
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材料科学
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DOI
高影响因子
CATALYSIS LETTERS
·
2024
·
IF 2.3
Mei Mingjie,Zhao Jiangui,Fang Hu,Sun Zuowei,Xue Weichao,Fu Haiyan,Li Ruixiang,Chen Hua,Li Chen,Yang Chunji,Zheng Xueli,Yuan Maolin
1,4-Butanediol, an important chemical raw material, especially as the monomer of engineering plastic polyethylene terephthalate (PBT), plays a pivotal role in contemporary chemicals. A promising parallel approach is the linear-selective hydroformylation of inexpensive allyl acetate, which is economical yet challenging. Herein, we describe an atom-economic approach characterized by high selectivity for synthesizing 4-oxobutyl acetate through rhodium-catalyzed hydroformylation using allyl acetate. This protocol affords the intermediate of valuable 1,4-butanediol in excellent yield (up to 95%) and exhibits excellent regioselectivity (linear/branched up to 164) under mild conditions (60 °C, 10 bar of syngas), effectively minimizing the formation of decomposed byproducts. The success of this protocol hinges on the use of a "Rh/POP-type ligand" in combination with either acetic acid or bulky anionic salts as additives. Preliminary mechanism studies show that the use of CH 3 COOH facilitates the formation of a tridentate κ 3 -P,O,P-coordination, which prevents the coordination of carbonyl with the Rh center, leading to the relatively high linear selectivity of 4-oxobutyl acetate. Furthermore, the successful application of this protocol in synthesizing 4-oxobutyl acetate at a scale of 3.8 g, employing low Rh-loading (0.05 mol%), highlights its potential for industrial applications. Graphical Abstract
研究领域:
化学工程
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催化化学
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DOI
高影响因子
JOURNAL OF CATALYSIS
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2024
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IF 6.5
Yue Ma,Ning Huang,Boyang Liu,Xiaocheng Lan,Xiaodong Wu,Tiefeng Wang
Styrene hydroformylation over Rh 2 P loaded on different oxides was compared to investigate support effects on catalytic performance. The electron density of Rh was probed by CO-DRIFTS, and the acid-base properties of the catalysts were detected by NH 3 - and CO 2 -TPD. Rh 2 P had higher electron density when loaded on basic supports, and n -type semiconductor showed additional electron donation effects compared to isolators. A kinetics model was established to identify hydrogen addition as the rate-determining step, and the changes in rate constant and adsorption equilibrium with different supports were compared. Electron donation from the supports was found to promote the activity of Rh 2 P via weakening styrene and aldehyde adsorption and facilitating hydrogen addition. The advantage of using CeO 2 ( i.e. , basic oxide with n -type semiconductivity) as the support was suggested.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-9
·
IF 16.6
Liu Yifeng,Liu Zhiqiang,Hui Yu,Wang Liang,Zhang Jian,Yi Xianfeng,Chen Wei,Wang Chengtao,Wang Hai,Qin Yucai,Song Lijuan,Zheng Anmin,Xiao Feng-Shou
Hydroformylation is one of the largest industrially homogeneous processes that strongly relies on catalysts with phosphine ligands such as the Wilkinson’s catalyst (triphenylphosphine coordinated Rh). Heterogeneous catalysts for olefin hydroformylation are highly desired but suffer from poor activity compared with homogeneous catalysts. Herein, we demonstrate that rhodium nanoparticles supported on siliceous MFI zeolite with abundant silanol nests are very active for hydroformylation, giving a turnover frequency as high as ~50,000 h −1 that even outperforms the classical Wilkinson’s catalyst. Mechanism study reveals that the siliceous zeolite with silanol nests could efficiently enrich olefin molecules to adjacent rhodium nanoparticles, enhancing the hydroformylation reaction.
研究领域:
催化化学
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材料科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2025
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IF 6.5
Li Huang,Jia Wang,Qi Liu,Peng Sun,Mengnan Nie,Guang Gao,Zelun Zhao,Zhiwei Huang,Fuwei Li
Olefin hydroformylation is one of the most important industrial processes for aldehyde synthesis. Heterogeneous catalysts are easy to separate compared with homogeneous catalysts, yet with limited success in activity and regioselectivity control. In the present work, a zeolite-encapsulated rhodium carbide species (RhC x @S-1) catalyst was developed, demonstrating not only relatively high catalytic activity but also good regioselectivity and stability in heterogeneous hydroformylation. The unique microenvironment of rhodium carbide species was formed in situ during the catalyst carbonization reduction process, tuning the steric and electronic characteristics of Rh species to obtain more linear aldehydes. This work shows an alternative strategy to promote the regioselectivity of olefin hydroformylation catalyzed by zeolite-confined catalysts and provides insights into the selective regulation of heterogeneous catalysts.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 39
·13955-13961
·
IF 4
Xiaorui Yan,Lele Chen,Haisheng Wei,Tiantian Liu,Kairui Li,Jing Li
The stability of Rh-based heterogeneous catalysts is a key issue in the hydroformylation of olefins. Confinement of active Rh species has been considered an effective strategy to achieve stable catalysts. In this work, a phosphine ligand was successfully confined in ZIF-8 material and coordinated with Rh metal by a reduction procedure to develop an efficient and stable Rh-based catalyst for hydroformylation of 1-octene. The results indicate that the catalyst reduced at 300 °C under H2 atmosphere exhibits better stability than that with NaBH4 as reductant and undoped P catalyst. Various characterization studies demonstrate that the superior performance is due to the strong interaction between Rh metal and P, which inhibits the leaching of active Rh species. This work reveals an effective strategy for the synthesis of highly stable catalysts for use in the hydroformylation reaction.
研究领域:
催化
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化学工程
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材料科学
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产品关联
DOI
PubMed
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Yuqing Wang,Miao Jiang,Li Yan,Cunyao Li,Guoqing Wang,Wenxiu He,Yunjie Ding
A series of porous organic polymer with different concentrations of tri(4-vinylphenyl)phosphite (P(OPh) 3 ) moieties were synthesized through the solvothermal synthesis technique. Their performance were investigated in 1-butene hydroformylation after metalation with metal species. The effect of the concentration of P(OPh) 3 moieties and pore structure of the polymers on catalytic efficiency were investigated in detail. The polymer-based Rh catalysts demonstrated a decrease in catalytic activity and inverse trends in selectivity with the increasing concentration of P(OPh) 3 . More importantly, Rh/POP-PhPh 3 -BP-P(OPh) 3 -x catalysts containing biphephos moieties exhibited more excellent catalytic performance than the corresponding Rh/POP-PhPh 3 -P(OPh) 3 -x catalysts. And the optimal catalytic performance, a valeraldehyde n/i ratio of 60.4, a valeraldehyde TOF of 9589.9 h −1 , and good catalytic stability were acquired for Rh/POP-PhPh 3 -BP-P(OPh) 3 –0.9 catalyst. The extraordinary catalytic properties are attributed to the formation of abundant active pentacoordinated hydridorhodium complexes, as demonstrated by in situ FT-IR experiments.
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
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