Small
·
2020
·Vol. 16
·期 10
·1906707
·
IF 11.459
Yunqing Kang,Joel Henzie,Huajun Gu,Jongbeom Na,Amanullah Fatehmulla,Belqes Saeed A. Shamsan,Abdullah M. Aldhafiri,W. Aslam Farooq,Yoshio Bando,Toru Asahi,Bo Jiang,Hexing Li,Yusuke Yamauchi
Selective hydrogenation of nitriles is an industrially relevant synthetic route for the preparation of primary amines. Amorphous metal–boron alloys have a tunable, glass-like structure that generates a high concentration of unsaturated metal surface atoms that serve as active sites in hydrogenation reactions. Here, a method to create nanoparticles composed of mesoporous 3D networks of amorphous nickel–boron (Ni-B) alloy is reported. The hydrogenation of benzyl cyanide to β-phenylethylamine is used as a model reaction to assess catalytic performance. The mesoporous Ni-B alloy spheres have a turnover frequency value of 11.6 h −1 , which outperforms non-porous Ni-B spheres with the same composition. The bottom-up synthesis of mesoporous transition metal–metalloid alloys expands the possible reactions that these metal architectures can perform while simultaneously incorporating more Earth-abundant catalysts.
研究领域:
材料科学
·
催化
·
化工
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Jia-qi Bai,Mei Ma,Huangfei Liu,Zhangkai Qian,Durui Liu,Yuncai Zhao,Yijing Gao,Jingshuai Chen,Mengdie Cai,Song Sun
The hydrogenation of nitriles is an environmentally friendly and atom-economical route to prepare high-value amines; however, it is still a challenge to control selectivity because of the occurrence of hydrogenation, self-coupling, and hydrogenolysis reactions during the hydrogenation process. It is highly desirable to develop efficient non-noble-metal catalysts for the hydrogenation of nitriles to secondary amines, although several noble metal catalysts have been reported. Herein, we successfully prepared a Cu–Ni/W20O58 catalyst and found that the Cu4.4–Ni0.6/W20O58 catalyst showed a 92.3% yield with initial TOFs of 270.0 h–1 at 373 K and 3 MPa H2 for the hydrogenation of benzonitrile (BN) to dibenzylamine (DBA), which was much superior to that of the monometallic Cu4.4/W20O58 and Ni0.6/W20O58 catalysts. Moreover, the Cu4.4–Ni0.6/W20O58 catalyst could be reused at least 4 times and was effective for the hydrogenation of various nitriles with superior selectivity to secondary amines. Furthermore, the reaction mechanism of BN hydrogenation for the Cu–Ni alloy of Cu4.4–Ni0.6/W20O58 was proposed on the basis of spectroscopic studies such as XRD, TPR, TEM, XAFS, and XPS, kinetic studies such as the effect of BN concentration and H2 pressure, the isotopic effect of hydrogen, and the effect of the reaction temperature and DFT calculations. The rate-determining step was the hydrogenation of benzylidenamine (BI) to the half-hydrogenated intermediate by one H atom over the Cu4.4–Ni0.6/W20O58 catalyst. The Ni–W20O58 interface was responsible for the adsorption and activation of BN, and the electron-rich Cu acted as the site for H2 dissociation; the synergistic effect of Cu and Ni led to the superior catalytic performance of the Cu4.4–Ni0.6/W20O58 catalyst.
研究领域:
催化化学
·
材料科学
·
环境化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2024
·Vol. 14
·期 1
·70
·
IF 3.8
Min Zhang,Hongwei Xiang,Xiaodong Wen
This investigation explores the synthesis of advanced catalysts for epoxidizing long-chain linear α-olefins, a pivotal process in the chemical industry for generating critical intermediates. Employing a hydrothermal technique, we developed four distinct catalysts (CS-1–4), methodically modulating the Ca/Sn ratio to elucidate its impact on the catalysts’ physicochemical properties. Our research uncovered that an escalated Ca/Sn ratio induces a morphological shift from octagonal to cubic structures, concomitant with a diminution in particle size and an enhancement in specific surface area. Significantly, the CS-3 catalyst outperformed others in 1-octene epoxidation, an efficacy attributed to its augmented surface alkalinity and proliferation of medium-strength alkaline sites, likely emanating from increased surface oxygen defects. Subsequent hydrogen reduction of CS-3 further amplified these oxygen defects, yielding a 10% uptick in catalytic activity. This correlation underscores the potential of oxygen defect manipulation in optimizing catalytic efficiency. Our findings contribute a novel perspective to the development of robust, high-performance catalysts for α-olefin epoxidation, seamlessly aligning with the principles of sustainable chemistry.Keywords:long-chain linear alpha-olefin;perovskite oxide;CaSnO3;oxygen vacancy;epoxidation
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 CHROMATOGRAPHY A
·
2024
·
IF 3.8
Yibo Yan,Ruilin Yang,Yanan Wang,Yinan Wu,Xiaofei Gu,Xiaoqiang Qiao
Styrene-maleic acid (SMA) copolymer has received much attention for its excellent solubilization characteristics. In this work, SMA copolymer brush-based chromatographic stationary phases were exploited and developed for the first time. First, SMA copolymer brush was in situ grown on the surface of spherical silica via living/controlled reversible addition-fragmentation chain transfer (RAFT) polymerization method. Subsequently, as a proof-of-concept demonstration, the copolymer was esterified by diethylene glycol mono-2-ethylhexyl ether (DGME) and 2-(2-ethylhexyloxy) ethanol (EHOE), respectively. The obtained Sil-SMA-DGME and Sil-SMA-EHOE copolymer-brush chromatographic stationary phases were characterized by transmission electron microscopy, Fourier transform infrared spectrometer, X-ray photoelectron spectroscopy, and thermogravimetric analysis, respectively. The chromatographic retention mechanism indicated that both the two packed columns exhibited hydrophilic/reverse mixed-mode retention modes. The maximum column efficiency was up to 71,000 N/m. The chromatographic separation performance evaluation indicated that the novel kind of stationary phases had excellent separation capabilities for hydrophilic, hydrophobic compounds and phospholipid standards. In addition, by combination with mass spectrometry identification, the Sil-SMA-DGME column was further exploited for separation and identification of phospholipids in human lung cancer cells. Totally, 9 classes including 186 phospholipid species were successfully identified. The results demonstrated the promising application prospects of the novel kind of SMA copolymer-brush chromatographic stationary phases.
研究领域:
分析化学
·
材料科学
·
生物技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FOOD CHEMISTRY
·
2025
·
IF 9.8
Run Liu,Yi Zhang,Yuanzhi Xu,Zhonghui Liu,Jinhang Chen,Kheng-Lim Goh,Yufei Zhang,Mingming Zheng
Diacylglycerol (DAG) is a functional lipid that is naturally present in vegetable oils in limited concentrations (1 %–5 %). This study proposed an enzymatic method to afford high-content-DAG vegetable oils via a reaction catalyzed by an immobilized lipase, PS@OMS-C 8 , using high-speed homogenization and molecular distillation. Results indicated that 48.6 % DAG was initially obtained through the enzymatic glycerolysis of rapeseed oil with glycerol, of which 90.2 % was sn -1,3-DAG. PS@OMS-C 8 maintained 35.5 % DAG content after 10 reuse cycles, confirming its catalytic stability; this was attributed to lipase immobilization on the ordered mesoporous silica that significantly improve the secondary protein structures, including α-helix and β-sheet, thereby strengthening the rigidity of PS@OMS-C 8 . In addition to producing DAG-enriched rapeseed oil, other edible oils with 39.4 %–50.2 % DAG content were obtained, as revealed via molecular docking simulation. This study offers new strategies for the sustainable synthesis of vegetable oils with a high content of functional lipids high-content functional lipids.
研究领域:
食品科学
·
生物化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2025
·
IF 2.1
Mingya Wang,Hongxia Pan,Yongzheng Liu,Jun Chen,Duanlin Cao,Linxiu Zhao
3(5)-Nitropyrazole is obtained by rearrangement of 1-nitropyrazole in high boiling organic solvents. In this paper, the solubility of 3(5)-nitropyrazole in 12 high boiling solvents (anisole, benzonitrile, mesitylene, o-dichlorobenzene, 1-octanol, benzyl alcohol, 2-ethylhexyl acetate, dimethyl glutarate, cyclohexanone, N,N-dimethylformamide, N-methylformamide, and isophorone) was determined using the static gravimetric method over the temperature range of 283.15–323.15 K. The experimental results revealed that the solubility of 3(5)-nitropyrazole exhibited a positive correlation with temperature. Under ambient conditions at 298.15 K, the solubility decreased in the following order: N,N-dimethylformamide (37.705 × 10–2), N-methylformamide (20.131 × 10–2), cyclohexanone (13.469 × 10–2), isophorone (11.957 × 10–2), dimethyl glutarate (6.667 × 10–2), benzyl alcohol (3.909 × 10–2), benzonitrile (2.915 × 10–2), 1-octanol (1.916 × 10–2), 2-ethylhexyl acetate (1.220 × 10–2), o-dichlorobenzene (0.666 × 10–2), anisole (0.688 × 10–2), and mesitylene (0.246 × 10–2). The solubility of 3(5)-nitropyrazole was fitted using the Apelblat equation, λh equation, NRTL model, and van’t Hoff model. The fitting results were evaluated using average relative deviation and RMSD. The NRTL model exhibited the best overall performance. The use of Hansen solubility parameters for solubility prediction and analysis has certain limitations.
研究领域:
化学工程
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
EES Catalysis
·
2025
·
IF 8.1
Ganchang Lei,Jiayin Wang,Xinhui Liu,Shiping Wang,Lijuan Shen,Shijing Liang,Yingying Zhan,Lilong Jiang
Developing efficient strategies that convert industrial waste hydrogen sulfide (H2S) into value-added products is meaningful for both applied environmental science and industrial chemistry. Here we report a series of heterogeneous N-doped carbon catalysts with synergistic C-N sites that enable the nucleophilic addition of H2S into aromatic nitrile compounds (PhCN) under mild conditions to produce thiobenzamide (PhCSNH2). The as-designed C-N sites achieve a high thioamide production rate of 26400 μmolPhCSNH2/L·h and a notable selectivity of ca. 80% at 60 °C within a short 2-hour timeframe. Additionally, the catalyst exhibits easy recyclability and maintains high stability over ten cycles during a 6-month period. Systematic microscopic and in situ spectroscopic characterizations, combined with theoretical calculations, reveal that C-pyridinic N coordination sites effectively lower the adsorption energy barrier of the crucial intermediate *PhCSHNH, offering a dynamically favorable pathway for PhCSNH2 production. Furthermore, the protocol demonstrates excellent compatibility with various substituted substrates, providing access to a diverse range of thioamides.
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Jiaxin Li,Ganceng Yang,Yanqing Jiao,Hongyan Sun,Jiaqi Wang,Yue Liu,Chungui Tian,Haijing Yan,Honggang Fu
Selective electroreduction of nitrobenzene (NB) to generate valuable azoxybenzene (AOB) is an important electrochemical N-N coupling reaction, but suffering from low selectivity at low potential. Herein, we constructed a Mo-incorporated NiFe bimetallic nitride on nickel foam (Mo-Fe 2 Ni 2 N/NF), effectively catalyzing selective electroreduction of NB (NSR) to generate AOB. Experimental and theoretical findings reveal that incorporating Mo into Fe 2 Ni 2 N triggers a rational charge redistribution, which induces a moderate hydrogen affinity, alongside enhances the adsorption of nitrosobenzene and phenylhydroxylamine intermediates so as to lower energy barrier of potential-determining step (PDS) for formation of AOB and higher energy barriers of PDS for formation of by-products (amine and azobenzene) can be achieved, thus leading to desired tandem reactions of partial hydrogenation reduction and bimolecular coupling for selective electrosynthesis of AOB. As a result, Mo-Fe 2 Ni 2 N/NF exerts an ultralow potential (0.341 V@100 mA cm −2 ) along with 100 % conversion of NB and 97.2 % yield of AOB. Remarkably, an anion exchange membrane flow electrolyzer of pairing cathodic NSR with anodic benzylamine oxidation by using Mo-Fe 2 Ni 2 N/NF cathode and Mo x Ni y N/NF anode is integrated, and simultaneous synthesis of value-added, easy-separation AOB and benzonitrile can be accomplished with low voltage (1.50 V@100 mA cm −2 ) and high productivity (> 90 %), highlighting its large potential for industrial application. This work showcases a new route to design efficient electrocatalysts for organic electrosynthesis via manipulating adsorption of key reaction species of constructing multicomponent nitrides.
研究领域:
材料科学
·
电化学
·
有机合成
✓ 已验证
产品关联
DOI
高影响因子
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
·
2025
·
IF 3.8
Yang Ruilin,Wang Ping,Guan Xinhui,Gu Xiaofei,Qiao Xiaoqiang
Phospholipids have been considered biomarkers for diagnosing many diseases in recent years. However, the isolation and analysis of phospholipids still face many difficulties. Styrene-maleic acid (SMA) copolymer is currently considered suitable for the separation and analysis of phospholipids due to its ability to enhance and improve the solubility of phospholipid bilayers on cell membranes. In this work, metal-free atom transfer radical polymerization was first exploited to graft SMA copolymer onto the surface of silica gel. With glycerol monolaurate (GML) as the derivatization reagent, Sil-SMA-GML polymer-brush silica-based stationary phase was first developed. The chromatographic retention mechanism revealed that the Sil-SMA-GML column is of hydrophilic/reversed-phase mixed-mode retention modes. The chromatographic separation performance evaluation indicated that the Sil-SMA-GML column had excellent separation capabilities for both hydrophilic and hydrophobic compounds. The maximum column efficiency was up to 78,600 N/m. The Sil-SMA-GML column could also achieve simultaneous separation and analysis of different phospholipid classes and species as well as complex phospholipid extracts from human serum and exosomal phospholipid extracts, demonstrating the good potential of the developed stationary phase. Graphical
研究领域:
分析化学
·
生物分离技术
·
材料科学
·
色谱学
·
生物医学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ANALYTICA CHIMICA ACTA
·
2026
·
IF 6.1
Ping Wang,Meijuan Xue,Xinhui Guan,Xiaofei Gu,Xiaoqiang Qiao
Background Phospholipids in serum exosomes are promising biomarkers for breast cancer diagnosis. However, the separation of phospholipids by liquid chromatography presents several challenges due to their inherent structural heterogeneity and the presence of isomeric forms. Traditional columns often struggle with the overlapping retention times of phospholipid species, which can result in poor resolution and difficulty in accurate quantification. Furthermore, the varying polarities and hydrophobicities of different phospholipid classes necessitate specialized stationary phases to achieve optimal separation. This study aimed to develop a novel chromatographic material for the comprehensive analysis of phospholipids in complex biological matrices. Results In this study, a novel silica-based Sil-SMA-GMS copolymer brush stationary phase was fabricated for the first time via reversible addition-fragmentation chain transfer (RAFT) polymerization, using styrene-maleic anhydride (SMA) copolymer as the functional matrix and glycerol monostearate (GMS) as the derivatization reagent. Benefiting from the synergistic effects of hydrophobic moieties (benzene rings and long alkyl chains) and hydrophilic groups (carboxyl and hydroxyl groups) in the SMA copolymer, the prepared stationary phase exhibited a unique mixed hydrophilic interaction chromatography/reversed-phase liquid chromatography (HILIC/RPLC) retention mechanism. It demonstrated excellent separation selectivity and stability for both hydrophilic and hydrophobic small molecules, achieving a maximum column efficiency of 81,029 N/m. Notably, this stationary phase overcame the limitations of traditional single-mode chromatographic columns, enabling the simultaneous separation and analysis of phospholipids that vary in class, acyl chain length, and degree of unsaturation. Furthermore, by coupling the Sil-SMA-GMS column with mass spectrometry (MS), a non-targeted analytical method for serum exosomal phospholipids was developed. Applying this method to serum exosomes from breast cancer patients and healthy controls led to the identification of 9 major classes encompassing 200 phospholipid molecular subtypes, as well as the screening of phospholipid markers closely associated with breast cancer pathogenesis. Significance This work presents a novel chromatographic material for the efficient separation of phospholipids in complex biological samples and establishes a technical foundation for the construction of multidimensional lipidomics platform. This advancement provides crucial support for the screening of cancer-related biomarkers, elucidating tumor metabolic mechanisms, and exploring targeted therapeutic targets.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
LANGMUIR
·
2025
·
IF 3.9
Chen Shen,Binyu Zhang,Haiyong Wang,Mi Luo,Tianhan Zhu,Tianyu Gao,Tong Zhang,Xiaoli Chen,Chenguang Wang
Precise modulation of interfacial electronic structures is crucial for enhancing the catalytic activity and selectivity in heterogeneous catalysis. The electron penetration effect (EPE), involving electron transfer from a metal core through a protective shell to surface active sites, has emerged as an effective strategy for tuning surface electronic properties and promoting catalytic performance. However, controlled manipulation of EPE remains challenging, particularly in regulating the phase structure of the metal core and the characteristics of the encapsulating shell. In this work, nitrogen-doped graphene-coated Ni nanoparticles were synthesized from a Ni-based metal–organic framework (Ni-MOF-T/t) by systematically adjusting the reduction temperature (T) and time (t). Subsequent deposition of Pd species yielded Pd/Ni-MOF-T/t catalysts. Among them, the optimized Pd/Ni-MOF-400 °C/2 h catalyst, featuring a hexagonal Ni core, exhibited enhanced electron penetration across the graphitic shell to the Pd sites, effectively modulating the surface electronic structure and boosting catalytic activity. The catalyst demonstrated excellent performance in both thermocatalytic hydrogenation of benzonitrile (90% conversion, 99.0% selectivity) and electrochemical hydrogenation of 4-nitrophenol (96.5% conversion, 90.5% Faradaic efficiency). These findings highlight that phase-controlled electron penetration provides a versatile and generalizable approach for constructing multifunctional catalysts with superior activity under mild conditions. This work establishes phase engineering of MOF-derived metal–carbon interfaces as an effective strategy to manipulate electron penetration effects and optimize catalytic performance.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nano Research
·
2024
·Vol. 17
·期 7
·6119-6126
·
IF 9.5
Li Ziwei,Yu Yue,Yang Dongyue,Wang Jin,Yan Junmin,Huang Gang,Liu Tong,Zhang Xinbo
Li-O 2 batteries with high energy density hold significant promise as next-generation energy storage systems. However, Li-O 2 batteries have poor cycling performance at high current densities and large capacities, primarily due to the high impedance caused by the instability of the lithium anode and the sluggish kinetics in the discharge products decomposition on the cathode. Herein, we investigated a bifunctional nitrile additive (2-methoxy benzonitrile (2-MBN)) with good chemical/electrochemical stability to improve the performances of Li-O 2 batteries. The 2-MBN could actively modify the anode by ensuring uniform Li + deposition and optimizing the composition of solid electrolyte interphase (SEI). Meanwhile, it could also facilitate the decomposition of discharge products by inducing the formation of sheet-like Li 2 O 2 , significantly reducing the battery charge overpotential. The bifunctional effects of 2-MBN for the anode and cathode enable Li-O 2 batteries to achieve a stable lifetime of 97 cycles at a current density of 600 mA·g −1 with a fixed capacity of 2000 mAh·g −1 , much better than that of Li-O 2 batteries without 2-MBN (28 cycles). The inclusion of 2-MBN provides an effective approach for attaining high-performance Li-O 2 batteries.
研究领域:
电化学
·
能源材料科学
✓ 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）