MOLECULES
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2023
·Vol. 28
·期 10
·4164
·
IF 4.6
Jassim Mohamed Hamed Al-Kurdhani,Huajun Wang
A series of supported CuO-based nanoparticle catalysts were prepared by the impregnation method and used for the synthesis of glycerol carbonate from glycerol and CO2in the presence of 2-cyanopyridine as a dehydrant and DMF as a solvent. The effects of supports (activated alumina, silicon dioxide, graphene oxide, graphene, and activated carbon), CuO loading amount, calcination temperature, and reaction parameters on the catalytic activity of the catalyst were investigated in detail. XRD, FTIR, SEM, BET, and CO2-TPD were used for the characterization of the prepared catalysts. It is found that CuO/Al2O3shows a higher catalytic activity, which depends on the CuO loading amount and calcination temperature. The surface area and number of basic sites of the catalyst exhibit a crucial effect on the catalytic activity of CuO/Al2O3. Furthermore, there is a synergistic effect between the catalyst and 2-cyanopyridine where the former has a higher activation ability for glycerol and the latter acts not only as a dehydrant, but also as a promoter for CO2activation. Recycling experiments reveal that this catalyst can be reused for at least five cycles without any inactivation. Based on the experiment results and FTIR characterization, a possible reaction mechanism for the carbonylation of glycerol and CO2is proposed.Keywords:glycerol;glycerol carbonate;carbon dioxide;2-cyanopyridine;CuO/Al2O3
研究领域:
催化化学
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材料科学
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环境化学
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产品关联
DOI
PubMed
高影响因子
Catalysts
·
2025
·Vol. 16
·期 1
·33
·
IF 4
Yao Li,Zaixiao Ren,Juan Bai,Keju Sun,Ziwei Song,Shaotong Song
This study systematically investigates how organic ligand modifications—chain length adjusting and functional group incorporation—regulate the catalytic performance of UiO-66 derivatives for CO2-to-dimethyl carbonate (DMC) conversion. Through multi-technique characterization (Py-IR, TGA, FT-IR, XPS, etc.) and catalytic tests, Lewis acid/basic sites (LAS/LBS), bulk defects and electron density effects were identified as the three key factors to govern the catalytic activity. The bulk defects were believed to enhance mass transfer. Notably, MOF-801 (shortest ligand) and UiO-66-Br (electron-withdrawing-Br) achieved the highest TOFs of 0.86 h−1and 1.10 h−1, respectively. While LAS/LBS and electron-rich Zr clusters promote methanol activation, defect-enhanced mass transfer dominated over electronic effects in boosting DMC yield. These insights highlight the tunability of MOFs for CO2utilization via rational ligand design.
研究领域:
材料化学
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催化
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二氧化碳利用
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金属有机框架材料（MOFs）
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可持续化学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Lei Dong,Yangyang Yuan,Shengjie Zhu,Peidong Li,Xiaomin Zhang,Yanping Chen,Lei Xu
Direct synthesis of dimethyl carbonate (DMC) using CO2 and methanol as raw materials is an environmentally friendly and promising route for recycling carbon sources from exhaust gases. Herein, well-constructed CeO2-based nanoparticle catalysts promoted by various Fe contents were synthesized via a facile co-precipitation method and demonstrated to be highly effective for direct DMC synthesis. The uniform doping of iron species in ceria lattice resulted in the formation of more surface oxygen vacancies, and thereby more coordinatively unsaturated surface metal cations and lattice oxygen anions were generated, which served as the Lewis acidic-basic sites required for the reaction. Based on in-situ DRIFTS results, it was deduced that the oxygen vacancies played a crucial role in activating CO2 to reactive bidentate carbonates and the formation of active terminal methoxy intermediates was also enhanced by Fe incorporation. Consequently, the maximum DMC yield of 3.84 mmol h-1 g-1 cat was obtained on Fe0.04Ce0.96Ox under relatively mild reaction conditions of 130 °C and 3.0 MPa. Additionally, in the tandem reaction system using 2-cyanopyridine (2-CP) as a dehydrating agent, the catalytic activity for 2-CP hydration was found to be closely associated with the total basicity of the catalysts, and in turn a higher hydration rate was more conducive to the DMC synthesis through enhancing in-situ water removal efficiency. As expected, the present work provides in-depth insights into the structure-performance relationship of Fe-modified ceria-based catalysts for direct DMC synthesis from CO2 and methanol, and offers meaningful guidance for the advancement of highly efficient catalysts.
研究领域:
化学工程
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环境科学
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2024
·
IF 15.7
Jielin Huang,Jie Wang,Haonan Duan,Songsong Chen,Junping Zhang,Li Dong,Xiangping Zhang
Catalysts for CO 2 value-added conversion have been extensively explored, but there is still a lack of systematic design for catalysts that achieve efficient CO 2 conversion under mild conditions. Herein, we explored a mesoporous CeO 2 single-crystal formed with the regulation of ionic liquids, which catalyzed the effective carbonylation reaction with CO 2 under mild reaction conditions. By altering the synthetic environment, a series of uniform mesoporous CeO 2 particles with atomically aligned single-crystal frameworks were constructed, which have different surface physicochemical properties and primary aggregation degree. The prepared mesoporous CeO 2 single-crystal achieved efficient activation of CO 2 and alcohols at 0.5 MPa CO 2 and 100 °C, and the CeO 2 -IL-M catalyst shows optimal catalytic performance in the synthesis of ethylene carbonate with 46.22 mmol g –1 h –1 , which was 50.6 times as high as that of the CeO 2 obtained without ionic liquids. Subsequently, the catalytic pathway and mechanism of carbonylation reaction with CO 2 on mesoporous CeO 2 single-crystal were studied via React-IR spectra and C 18 O 2 labeling experiments. The research provides a new strategy for controllable nanoscale assembly of mesoporous single-crystal materials and expands the application range of single-crystal materials, aiming to develop novel catalytic materials to meet industrial needs.
研究领域:
材料科学
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催化化学
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环境科学
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产品关联
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2024
·
IF 6.1
Chengkun Bai,Bingdi Wang,Zhengshun Jiang,Chunying Lv,Zhenning Liu,Shiyu Wang,Song Liang,Hongying Zang
Inspired by the ordered processes of chloroplasts in photosynthesis involving coordinative linkages and efficient compartmentalization, a bioinspired compartmentalized photocatalytic system (BCPS) with an inorganic compartment is designed for photocatalytic hydrogen evolution with light driven electron carrier mediated cross-membrane energy transport. A typical BCPS comprises silica colloidosomes containing co-catalysts as microreactors, where positively charged N-methyl-4-cyanopyridinium (MCP+) serves as the electron carrier. The MCP+ molecules harvest energy from photoexcited g-C3N4, and transit to electrically neutral species MCP0, which can pass the colloidosome. Driven by light, the MCP0 diffuse across the membrane and transport electrons to H+ for hydrogen evolution, in which Pt particles are employed as co-catalysts. Analogous to natural photosynthesis, hydrogen evolution occurs within compartments, separating light and dark reactions, protecting the dark reaction from interference during light harvesting and minimizing potential side effects. The system enables sustained evolution of hydrogen with a higher yield than that with the control catalysis in a bulk catalyst suspension. The dramatic influence of SDS on the hydrogen evolution was revealed, and a possible mechanism of electron carrier amount buffering was proposed.
研究领域:
化学
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材料科学
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仿生学
✓ 已验证
产品关联
DOI
高影响因子
Coatings
·
2025
·Vol. 15
·期 6
·635
·
IF 2.8
Fan Cao,Shumei Yao,Xiaowen Meng,Jianpeng Wang,Sujie Chang,Yi Wang,Aiqing Song,Dayong Li,Lei Shi
The novel pyridine oxime-based complexing agents 2-pyridinecarboxaldehyde oxime, 2-acetylpyridine ketoxime and 2-pyridine amidoxime were synthesized for alkaline Zn-Ni alloy electrodeposition, outperforming conventional citrate/TEPA systems in corrosion resistance and microstructural control. The N,O-bidentate chelation mechanism governs metal ion reduction kinetics via diffusion-limited pathways, enabling γ-phase Ni5Zn21intermetallic formation and nanocrystalline refinement. Electrochemical and microstructural analyses demonstrate suppressed random nucleation and hydrogen evolution side reactions, leading to enhanced charge transfer resistance and reduced corrosion current density. Notably, 2-pyridine amidoxime achieves ultrasmooth surfaces through defect-free nanocluster growth, while 2-pyridinecarboxaldehyde oxime maximizes γ-phase crystallinity. The synergy between grain boundary density and surface integrity establishes a dual protection mechanism combining barrier layer formation and active dissolution suppression. This work advances microstructure engineering via coordination chemistry, offering a breakthrough over traditional zincate electroplating for high-performance anti-corrosion coatings.
研究领域:
材料科学
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电化学
·
表面工程
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2024
·
IF 15.7
Lei Dong,Shengjie Zhu,Yangyang Yuan,Xiaomin Zhang,Xiaowei Zhao,Yanping Chen,Lei Xu
The direct synthesis of dimethyl carbonate (DMC) from CO 2 and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes. Herein, a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO 2 and methanol, and the structure-performance relationship was investigated in detail. Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies indicated that the adsorption rate of methanol is slower than that of CO 2 and the methanol activation state largely influences the formation of key intermediate. Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO 2 , the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation. Moreover, with the use of 2-cyanopyridine as a dehydration reagent, the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
Journal of Inorganic and Organometallic Polymers and Materials
·
2020
·Vol. 30
·期 11
·4569-4577
·
IF 1.941
Zhou Lei,Qiu Jiaqi,Wang Maolin,Xu Zhenkai,Wang Jiping,Chen Tao
Abstract Polymer-based nanoreactor, which can be achieved by self-assembling of amphiphilic polymers in water, has attracted more and more attention in recent years. In this study, a kind of Pd-nanoreactor was fabricated by self-assembling of chiral palladium complex-containing amphiphilic polymers in water. Firstly, chain transfer reagent (CTA) CEPA-PyOx was obtained by condensation reaction of (S,S)-4-hydroxymethyl-5-phenyl-2-(2′-pyridinyl)-1,2-oxazoline (PyOx) and 4-cyano-4-[((ethylthio)carbonothioyl)thio] pentanoic acid (CEPA) in the presence of EDC·HCl. Next, polymethacrylate with a terminal chiral oxazoline ligand (CEPA-POEGMA 36 -PyOx) was synthesized through Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization. After removal of the thioester bond and coordination with palladium trifluoroacetate, the polymer self-assembled in water affording Pd-nanoreactor, which possess core-shell structure and with chiral palladium complex in the core. At last, the nanoreactor was successfully applied in the asymmetric catalytic synthesis of flavanone in aqueous phase, and the catalyst loading was greatly reduced compared to unsupported palladium complex. In the presence of low palladium loading (0.5 mol%), flavanone was successfully synthesized with excellent yield (98%) and high enantioselectivity (82%). Graphic Abstract
研究领域:
高分子化学
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催化化学
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材料科学
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产品关联
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2019
·Vol. 6
·期 4
·1040-1049
·
IF 5.934
Yi-Gang Wu,Dong-Bo Wang,Juan-Juan Hu,Xue-Qing Song,Cheng-Zhi Xie,Zhong-Ying Ma,Jing-Yuan Xu
The design, synthesis, crystal structures and in vitro biological assessment of three iron(III) complexes, namely [Fe(L1)2]Cl (1), [Fe(L2)2]·FeCl4 (2) and [Fe(L3)(HL3)2]·(FeCl4)2·(CH3OH) (3) (HL1 = N’-(4-oxothiazolidin-2-ylidene)picolinohydrazonamide, HL2 = 2-(2-(1-(pyridin-2-yl)ethylidene)hydrazono)thiazolidin-4-one, HL3 = 3-ethyl-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazono)thiazolidin-4-one, are reported in this article. Single crystal X-ray diffraction revealed that all three complexes were mononuclear molecules, approaching a coordination polyhedron of octahedral geometry, in which the 4-thiazolidinone derivative ligands exhibited different coordination modes and conformations. Their interactions with DNA were investigated by UV–visible and fluorescence spectrometries, and by agarose gel electrophoresis. Results indicated that they presented efficient DNA binding propensities and cleavage activities. In vitro, the iron(III) complexes caused cell cycle arrest at the G1 phase in response to DNA damage, effectively inhibited the cyclinD1 expression and decreased the migration of HeLa cells with a lower wound-healing rate than that of the control. Complex 3 was the most sensitive to HeLa cancer cells, followed by 2 and 1. Attractively, the tested complexes demonstrated significantly enhanced selectivity index values determined for HeLa vs. LO2 normal cells compared with cisplatin, especially for complex 3, which was up to 13.94-fold. Unlike cisplatin, more complex 3 would accumulate in HeLa cancer cells compared with LO2 normal cells.
研究领域:
无机化学
·
药物化学
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肿瘤学
·
分子生物学
·
生物化学
✓ 已验证
产品关联
DOI
高影响因子
Coatings
·
2021
·Vol. 11
·期 11
·1396
·
IF 2.881
Min Zhang,Dong Peng,Feifei Peng,Anwei Huang,Kaiqiang Song,Qingbing He,Changqing Yin,Jinsong Rao,Yuxin Zhang,Haitao Chen,Dalong Cong,Zhongsheng Li
The Al coatings were electrodeposited on the Cu substrate from AlCl3-EMIC ionic liquid (AlCl3:EMIC = 2:1 molar ratio) containing three cyanopyridine additives with different positions of the substituent group on the pyridine ring, which were 2-cyanopyridine, 3-cyanopyridine, and 4-cyanopyridine. The effects of cyanopyridine additives on the deposition potential, morphology, brightness, and corrosion properties of Al coatings were investigated. It was considered that the deposition potential of Al shifted to more negative overpotentials, the quality of Al coatings was promoted, and the corrosion property was improved by the cyanopyridine additives to a varying degree. Especially in the presence of 4-cyanopyridine, the flattest mirror bright Al coating was obtained, which had the smallest homogeneous nanocrystal grain size and strongest Al (200) crystallographic orientation. The average roughness Ra value was as low as 31 nm compared to that in the absence of cyanopyridine additives, which was 417 nm. Furthermore, the corrosion current density of the bright Al coating was three orders of magnitude lower than the rough Al coating, which resulted from the dense nanocrystal structure.Keywords:bright Al;electrodeposition;ionic liquids;cyanopyridine;additives
研究领域:
材料科学
·
电化学
·
表面工程
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Yangyang Sun,Zhuzhu Tang,Tingze Pan,Ke Zhang,Liuzhu Wang,Xingye Zhai,Yiran Jia,Tianqi Yuan,Yujia Qian,Hualei Wang,Dongzhi Wei,Shengli Yang
Catalytic promiscuity makes nitrilase-mediated unnatural reactivity a promising pathway in the production of primary amides . However, during the functional switch of nitrilase, a trade-off between the newly developed hydration activity and relative activity hinders the application of nitrilase in the production of amides. Our previous study showed that the mutant F193N (Mut0) of nitrilase NIT6803 from Synechocystis sp. PCC6803 improved the hydration activity as the amide ratio increased to 73.4%, whereas the relative activity was only 50.1% of that of the wild-type (WT). In this study, we succeeded in alleviating the trade-off of Mut0 through an evolutionary combination of the key identified sites 101, 192, and 201. Inside the active pocket, the co-evolution of residue Q192 was identified by hotspot prediction to correlate with N193, and Q192H exhibited an improved amide ratio of 76.9% with a relative activity of up to 72%. Outside the active pocket, the flexible loop surface residue G101 and homodimer “A” interface residue I201 were identified using sequence alignment-based mutations. Further evolutionary combination of the three key sites yielded the best triple mutant G101K/Q192H/I201M, which had the highest amide ratio of 98.5% and considerably recovered relative activity of 82.6% while retaining only 1.5% of the carboxylic acid ratio. The transition-state analogue sheds light on the basis of the almost identical switch of the reaction pathways, and our results expand the toolbox of nitrilase-catalysed promiscuity for amide formation.
研究领域:
生物化学
·
酶工程
✓ 已验证
产品关联
DOI
高影响因子
BIOORGANIC CHEMISTRY
·
2023
·
IF 5.1
Yangyang Sun,Zhuzhu Tang,Yanjun Li,Yongkang Song,Hualei Wang,Dongzhi Wei,Shengli Yang
Hydration, a secondary activity mediated by nitrilase, is a promising new pathway for amide production. However, low hydration activity of nitrilase or trade-off between hydration and catalytic activity hinders its application in the production of amides. Here, natural C-terminal-truncated wild-type nitrilase, mined from a public database, obtained a high-hydration activity nitrilase as a novel evolutionary starting point for further protein engineering. The nitrilase Nit-74 from Spirosoma linguale DSM 74 was successfully obtained and exhibited the highest hydration activity level, performing 50.7 % nicotinamide formation and 87.6 % conversion to 2 mM substrate 3-cyanopyridine. Steric hindrance of the catalytic activity center and the N -terminus of the catalytic cysteine residue helped us identify three key residues: I166, W168, and T191. Saturation mutations resulted in three single mutants that further improved the hydration activity of N -heterocyclic nitriles. Among them, the mutant T191S performed 72.7 % nicotinamide formation, which was much higher than the previously reported highest level of 18.7 %. Additionally, mutants I166N and W168Y exhibited a 97.5 % 2-picolinamide ratio and 97.7 % isonicotinamide ratio without any loss of catalytic activity, which did not indicate a trade-off effect. Our results expand the screening and evolution library of promiscuous nitrilases with high hydration activity for amide formation.
研究领域:
生物化学
·
分子生物学
·
酶工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）