Metal-Organic Catalyst for High Performance Materials

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Nanostructured Catalysts".

Deadline for manuscript submissions: closed (30 November 2023) | Viewed by 8598

Special Issue Editors

1. PetroChina Petrochemical Research Institute, Beijing 102206, China
2. Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Interests: transition metal complex; olefin polymerization; catalytic performance; molecular modeling; quantitative structure-property relationship; machine learning
Department of Chemistry, University of Massachusetts Amherst, Amherst, MA 01003, USA
Interests: density functional theory and time-dependent density functional theory; mechanism of homogeneous and heterogeneous catalytic reaction; excited state dynamic and photochemistry
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China
Interests: transition metal; machine learning; reaction mechanism; quantum tunneling; electronic structure

Special Issue Information

Dear Colleagues,

Metal-organic catalysts play a dominant role in chemistry and have become the power source of the chemical industry and material science. In the era of big data and intelligence, integration and efficiency have become the main theme of social development. Chemical manufacturing and material properties depend on the transformation and control of atomic bonding and functional groups in products, as well as the reduction in procedures and post-processing in the preparation process. Metal-organic catalysis provides the principles and methods for designing and synthesizing new molecules and functional groups, provides stable information recording and intelligent optimization of substrates, and helps to improve the performance and preparation efficiency of materials in order to meet the needs of high-performance and cost-effective materials for social development.

The present Special Issue will publish papers covering various areas in both academic research and industrial developments of catalyst design as well as catalytic transformation and industrialization. Authors have full flexibility concerning the form of contributions: full papers are preferred, but proposals for review or communication papers are welcome as well.

Dr. Wenhong Yang
Dr. Jun Yi
Dr. Zhifeng Ma
Guest Editors

Manuscript Submission Information

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Keywords

  • metal-organic catalyst
  • homogenous catalysis
  • heterogenous catalysis
  • polyethylene polymerization
  • ring-opening polymerization
  • isoprene polymerization
  • copolymerization
  • metathesis catalyst
  • polyester
  • polycarbonate
  • theoretical calculation

Published Papers (7 papers)

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Research

16 pages, 2683 KiB  
Article
Structurally Rigid (8-(Arylimino)-5,6,7-trihydroquinolin-2-yl)-methyl Acetate Cobalt Complex Catalysts for Isoprene Polymerization with High Activity and cis-1,4 Selectivity
by Nighat Yousuf, Yanping Ma, Qaiser Mahmood, Wenjuan Zhang, Ming Liu, Rongyan Yuan and Wen-Hua Sun
Catalysts 2023, 13(7), 1120; https://doi.org/10.3390/catal13071120 - 18 Jul 2023
Cited by 8 | Viewed by 881
Abstract
A series of cobalt complexes bearing (8-(arylimino)-5,6,7-trihydroquinolin-2-yl)methyl acetate ligand framework were prepared using a one-pot synthesis method. These complexes were then extensively investigated for their catalytic performance in isoprene polymerization. In addition to the complexes being characterized via FT-IR spectrum and elemental analysis, [...] Read more.
A series of cobalt complexes bearing (8-(arylimino)-5,6,7-trihydroquinolin-2-yl)methyl acetate ligand framework were prepared using a one-pot synthesis method. These complexes were then extensively investigated for their catalytic performance in isoprene polymerization. In addition to the complexes being characterized via FT-IR spectrum and elemental analysis, the molecular structure of Co1 and Co5 was determined via X-ray diffraction analysis. The analysis revealed a chloride-bridged centrosymmetric binuclear species in which each cobalt center exhibited a distorted square pyramidal geometry. Among the prepared complexes, Co1 demonstrated the highest catalytic activity of 1.37 × 105 g (mol of Co)−1(h)−1, achieving complete monomer conversion and resultant polyisoprene showed high molecular weight (Mn ≥ 2.6 × 105 g/mol). All of the complexes showed preference for the cis-1,4 configuration ranging from 65% to 72%, while the 3,4 monomer insertion units constituted between 27% and 34% of the polymer structure. Moreover, extensive investigations were conducted to assess the impact of reaction parameters and ligand properties on the catalytic activities and microstructural characteristics of the resulting polymer. Full article
(This article belongs to the Special Issue Metal-Organic Catalyst for High Performance Materials)
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15 pages, 3696 KiB  
Article
A DFT Study of the Copolymerization of Methyl Vinyl Sulfone and Ethylene Catalyzed by Phosphine–Sulfonate and α-Diimine Palladium Complexes
by Ling Zhu, Shuang Li, Xiaohui Kang, Wenzhen Zhang and Yi Luo
Catalysts 2023, 13(6), 1026; https://doi.org/10.3390/catal13061026 - 20 Jun 2023
Viewed by 935
Abstract
Density functional theory (DFT) calculations were comparatively carried out to reveal the origins of different catalytic performances from phosphine–benzene sulfonate (A, [{P^O}PdMe(L)] (P^O = Κ2-P,O-Ar2PC6H4SO3 with Ar = 2-MeOC6H4 [...] Read more.
Density functional theory (DFT) calculations were comparatively carried out to reveal the origins of different catalytic performances from phosphine–benzene sulfonate (A, [{P^O}PdMe(L)] (P^O = Κ2-P,O-Ar2PC6H4SO3 with Ar = 2-MeOC6H4)) and α-diimine (B, [{N^N}PdMe(Cl)] (N^N = (ArN=C(Me)-C(Me)=NAr) with Ar = 2,6-iPr2C6H3)) palladium complexes toward the copolymerization of ethylene and methyl vinyl sulfone (MVS). Having achieved agreement between theory and experiment, it was found that the favorable 2,1-selective insertion of MVS into phosphine–sulfonate palladium complex A was due to there being less structural deformations in the catalyst and monomer. Both the MVS and ethylene insertions were calculated, and the former was found to be more favorable for chain initiation and chain propagation. In the case of α-diimine palladium system B, the resulting product of the first MVS insertion was quite stable, and the stronger O-backbiting interaction hampered the insertion of the incoming ethylene molecule. These computational results are expected to provide some hints for the design of transition metal copolymerization catalysts. Full article
(This article belongs to the Special Issue Metal-Organic Catalyst for High Performance Materials)
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16 pages, 8042 KiB  
Article
Novel Brønsted Acidic Ionic Liquids as High Efficiency Catalysts for Liquid-Phase Beckmann Rearrangement
by Chunxiao Ren, Zhiyuan Wang, Qingwei Gao, Jisheng Li, Siqi Jiang, Qizhong Huang, Ye Yang, Jiahui Zhang, Yajing Wang, Yufeng Hu, Zhichang Liu and Xin Guo
Catalysts 2023, 13(6), 978; https://doi.org/10.3390/catal13060978 - 06 Jun 2023
Cited by 1 | Viewed by 1105
Abstract
Exploring environmentally friendly, efficient, cheap and recyclable catalysts are essential for the development of green, sustainable and mild processes for the liquid-phase Beckmann rearrangement. Herein, a novel caprolactam-based Brønsted acidic ionic liquid ([CPL][2MSA]) was developed for the conversion of cyclohexanone oxime (CHO) to [...] Read more.
Exploring environmentally friendly, efficient, cheap and recyclable catalysts are essential for the development of green, sustainable and mild processes for the liquid-phase Beckmann rearrangement. Herein, a novel caprolactam-based Brønsted acidic ionic liquid ([CPL][2MSA]) was developed for the conversion of cyclohexanone oxime (CHO) to caprolactam (CPL), not only as a catalyst, but also as a mild reaction medium. Under the reaction conditions for the reaction temperature (90 °C), reaction time (2 h) and mole ratio ([CPL][2MSA]: CHO = 3:1), [CPL][2MSA] possesses plenty of high sulfonate groups, which exhibit high conversion (100%) and selectivity (95%) without any other co-catalysts or metals. Based on the thermogravimetric (TGA) and differential scanning calorimetry (DSC) analyses, the decomposition and glass transition temperatures are gradually increased with the increase in MSA mole content, revealing the existence of hydrogen-bonded clusters. Interestingly, the occurrent route of the liquid-phase Beckmann rearrangement for CHO in [CPL][2MSA] is revealed by in situ FT-Raman. In addition, the dominating H-bond combination between CHO and [CPL][2MSA] is further confirmed by COSMO-RS model. The activation energy (Ea) of the reaction is calculated by the first-order reaction kinetics. Thus, the [CPL][2MSA] with plenty of acidic catalytic active species is an environmentally friendly and efficient candidate for the liquid-phase Beckmann rearrangement. Full article
(This article belongs to the Special Issue Metal-Organic Catalyst for High Performance Materials)
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21 pages, 3696 KiB  
Article
Isoselective Ring-Opening Polymerization of rac-Lactide Catalyzed by Simple Potassium Amidate Complexes Containing Polycyclic Aryl Group
by Jiahao Gao, Wenjuan Zhang, Xing Wang, Rui Wang, Mingyang Han, Furong Cao and Xiang Hao
Catalysts 2023, 13(4), 770; https://doi.org/10.3390/catal13040770 - 19 Apr 2023
Viewed by 1199
Abstract
The isoselective ring-opening polymerization of rac-LA is a challenging goal. In this work, a series of potassium amidate complexes (K1K10) were easily prepared and characterized using the 1H/13C NMR spectrum. The molecular structures of potassium [...] Read more.
The isoselective ring-opening polymerization of rac-LA is a challenging goal. In this work, a series of potassium amidate complexes (K1K10) were easily prepared and characterized using the 1H/13C NMR spectrum. The molecular structures of potassium complexes K2 and K10 were determined by X-ray diffraction, which showed that both were two-dimensional coordination polymers due to the adjacent π interactions of the aryl. In the presence of benzyl alcohol (BnOH), all of the potassium complexes exhibited a high catalytic activity toward the ring-opening polymerization of L-lactide and rac-LA, yielding linear polylactides capped with BnO or CH3O end groups. A significant solvent effect on the ROP of the L-LA was observed, with a superior efficiency in toluene than in THF and CH2Cl2. These complexes are iso-selective and act as active catalysts for the controlled ring-opening polymerization of rac-lactide, with a Pm from 0.54 to 0.76. This is a rare example of simple alkali metal complexes for the isoselective ROP of rac-lactide. The substituent greatly affected the monomer conversion and isoselectivities. Full article
(This article belongs to the Special Issue Metal-Organic Catalyst for High Performance Materials)
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7 pages, 3113 KiB  
Article
Ruthenium Metathesis Catalysts with Imidazole Ligands
by Peng Ma, Jiaren Zhang, Xiaqian Wu and Jianhui Wang
Catalysts 2023, 13(2), 276; https://doi.org/10.3390/catal13020276 - 26 Jan 2023
Cited by 1 | Viewed by 1393
Abstract
Phosphine-free ruthenium benzylidene complexes containing imidazole ligands are reported. These catalysts are effective for ring-closing metathesis (RCM) and cross-metathesis (CM) reactions at high temperatures, where the more widely used phosphine-containing N-heterocyclic carbene-based ruthenium catalysts show side reactions. This discovery opens up a [...] Read more.
Phosphine-free ruthenium benzylidene complexes containing imidazole ligands are reported. These catalysts are effective for ring-closing metathesis (RCM) and cross-metathesis (CM) reactions at high temperatures, where the more widely used phosphine-containing N-heterocyclic carbene-based ruthenium catalysts show side reactions. This discovery opens up a pathway to develop more selective ruthenium metathesis catalysts for reactions requiring harsh conditions. Full article
(This article belongs to the Special Issue Metal-Organic Catalyst for High Performance Materials)
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11 pages, 2208 KiB  
Communication
Single-Atom Iron Catalyst Based on Functionalized Mesophase Pitch Exhibiting Efficient Oxygen Reduction Reaction Activity
by Xianrui Gu, Meng Wang, Hongpeng Peng, Qian Peng, Wei Wang, Houpeng Wang, Junjun Shi, Xuetao Qin, Zhijian Da, Wenhong Yang, Yuchao Wu, Ding Ma and Houliang Dai
Catalysts 2022, 12(12), 1608; https://doi.org/10.3390/catal12121608 - 08 Dec 2022
Viewed by 1308
Abstract
Designing highly efficient and low-cost electrocatalysts is of great importance in the fields of energy conversion and storage. We report on the facile synthesis of a single atom (SA) iron catalyst via the pyrolysis of a functionalized mesophase pitch. Monomers of naphthalene and [...] Read more.
Designing highly efficient and low-cost electrocatalysts is of great importance in the fields of energy conversion and storage. We report on the facile synthesis of a single atom (SA) iron catalyst via the pyrolysis of a functionalized mesophase pitch. Monomers of naphthalene and indole underwent polymerization in the presence of iron chloride, which afterwards served as the pore-forming agent and iron source for the resulting catalyst. The SA-Fe@NC catalyst has a well-defined atomic dispersion of iron atoms coordinated by N-ligands in the porous carbon matrix, exhibiting excellent oxygen reduction reaction (ORR) activity (E1/2 = 0.89 V) that outperforms the commercial Pt/C catalyst (E1/2 = 0.84 V). Moreover, it shows better long-term stability than the Pt/C catalyst in alkaline media. This facile strategy could be employed in versatile fossil feedstock and develop promising non-platinum group metal ORR catalysts for fuel cell technologies. Full article
(This article belongs to the Special Issue Metal-Organic Catalyst for High Performance Materials)
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21 pages, 2391 KiB  
Article
Electronic Tuning of Sterically Encumbered 2-(Arylimino)Pyridine-Nickel Ethylene Polymerization Catalysts by Para-Group Modification
by Zahra Hosseinzadeh, Ming Liu, Qiuyue Zhang, Tongling Liang, Gregory A. Solan, Yanping Ma and Wen-Hua Sun
Catalysts 2022, 12(12), 1520; https://doi.org/10.3390/catal12121520 - 25 Nov 2022
Cited by 1 | Viewed by 1073
Abstract
A collection of five related 2-(arylimino)pyridines, 2-{(2,6-(CH(C6H4-p-F)2)2-4- RC6H2)N=CMe}C5H4N, each ortho-substituted with 4,4′-difluorobenzhydryl groups but distinct in the electronic properties of the para-R substituent [...] Read more.
A collection of five related 2-(arylimino)pyridines, 2-{(2,6-(CH(C6H4-p-F)2)2-4- RC6H2)N=CMe}C5H4N, each ortho-substituted with 4,4′-difluorobenzhydryl groups but distinct in the electronic properties of the para-R substituent (R = Me L1, Et L2, i-Pr L3, F L4, OCF3 L5), were prepared and combined with (DME)NiBr2 to form their corresponding LNiBr2 complexes, Ni1Ni5, in high yields. All the complexes were characterized by FT-IR, 19F NMR spectroscopy and elemental analysis, while Ni5 was additionally the subject of an X-ray determination, revealing a bromide-bridged dimer. The molecular structure of bis-ligated (L4)2NiBr2 (Ni4’) was also determined, the result of ligand reorganization having occurred during attempted crystallization of Ni4. On activation with either EtAlCl2 or MMAO, Ni1Ni5 exhibited high catalytic activities (up to 4.28 × 106 g of PE (mol of Ni)−1 h−1 using EtAlCl2) and produced highly branched polyethylene exhibiting low molecular weight (Mw range: 2.50–6.18 kg·mol−1) and narrow dispersity (Mw/Mn range: 2.21–2.90). Notably, it was found that the type of para-R group impacted on catalytic performance with Ni5 > Ni4 > Ni3 > Ni1 > Ni2 for both co-catalysts, underlining the positive influence of electron withdrawing substituents. Analysis of the structural composition of the polyethylene by 1H and 13C NMR spectroscopy revealed the existence of vinyl-end groups (–CH=CH2) and high levels of internal unsaturation (–CH=CH–) (ratio of vinylene to vinyl, range: 3.1:1–10.3:1) along with various types of branch (Me, Et, Pr, Bu, 1,4-paired Me, 1,6-paired Me and LCBs). Furthermore, reaction temperature was shown to greatly affect the end group type, branching density, molecular weight and in turn the melting points of the resulting polyethylenes. Full article
(This article belongs to the Special Issue Metal-Organic Catalyst for High Performance Materials)
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