Reaction Kinetics Mechanisms and Catalysis
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2024
·Vol. 137
·期 4
·1911-1925
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IF 1.7
Song Linyan,Nie Genkuo,Chen Xiulei,Wang Hongyu,Liu Shiwei,Yu Hailong,Liu Xuguang,Yang Guihua,Yu Shitao
The multifunctional groups of 5-hydroxymethylfurfural (5-HMF) make it could extend carbon chain by different C–C coupling reactions and extensively applied in the bio-jet fuel synthesis. Herein, one-pot reaction of lignocellulose derived chemicals with 5-HMF was studied by experimental and density functional theory (DFT) methods. The kinetic models of products were established and the apparent activation energies of the products by C–C coupling reaction of phenol, anisole, guaiacol, cyclohexanone and acetone with 5-HMF on Hβ were 95.3 kJ/mol, 104.8 kJ/mol, 90.4 kJ/mol, 90.0 kJ/mol and 112.2 kJ/mol, indicating these reactions centering on 5-HMF competitive intensively. Then the effects of the catalysis were analyzed by applying commercial catalysis to the mixed coupling reaction of 5-HMF. It was found that Brønsted acid is more favorable to alkylation reaction, and Lewis acid is more beneficial to aldol condensation reaction. By Fukui function, due to the nucleophilic index of cyclohexanone (2.74 eV) is higher than that (2.48 eV) of acetone, and the Mulliken electronegativity (3.43 eV) is weaker than that (3.55 eV) of acetone, cyclohexanone is more conducive than acetone to the aldol condensation reaction. This work provides data reference for product regulation in the bio-jet fuel synthesis.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Wei Wei,Zhenyao Li,Jitao Shang,Chenxi Xia,Xuli Hu,Yangshun Hu,Junchen Xu,Yan Zhao,Mingyue Ding
The selective electrochemical reduction of CO to valuable multi-carbon (C 2 + ) products is a key strategy for mitigating global warming and addressing the energy crisis. Nevertheless, the activity and selectivity of CO-to-C 2+ products conversion remain low due to the lack of effective catalysts. In this study, bimetallic CuPd was grown in situ on Cu nanoparticles via a seed-mediated approach, constructing a stable CuPd/Cu interface for the CO reduction reaction (CORR). The CuPd alloy promotes CO adsorption and hydrogenation, resulting in abundant and stable *COH intermediates over catalytic sites. Consequently, a stable asymmetric coupling is established at the CuPd/Cu interface, lowering the reaction energy barrier and facilitating C-C coupling. A high acetate selectivity of 49 % was achieved at –1.0 V versus the reversible hydrogen electrode (RHE) with a current density of 349 mA/cm². This study highlights the critical role of constructing CuPd/Cu asymmetric sites for C–C coupling, paving the way for designing highly selective catalysts that enhance C 2+ product formation and acetate production.
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Surfaces and Interfaces
·
2024
·
IF 5.7
Zhixiu Yang,Xiaoxuan Guo,Yong Chen,Lijing Gao,Ruiping Wei,Guomin Xiao
Modulating the surface microenvironment is crucial in strengthening C C coupling, leading to increasing selectivity in the production of multi-carbon (C 2+ ) products during CO 2 electroreduction. Herein, we have concentrated on investigating how to control the effect of surface distribution of active components of a series of Ag-decorated CuO , denoted as xAg/yCuO. These catalysts with similar chemical elements and morphology are designed, but they exhibit different selectivity in the CO 2 electroreduction process. As a result, the Ag particles in 3Ag/CuO aggregates, while the Ag in 2Ag/2CuO and Ag/3CuO is uniformly distributed on the flower-like CuO nanosphere . Besides, 3Ag/CuO has the highest Faraday efficiency (FE) of CO with a value of 30.9 % at 0.8 V vs. RHE, demonstrating rich-Ag catalysts are beneficial to produce CO. 2Ag/2CuO shows excellent FE C2H4 of 51.4 % at -1.2 V vs. RHE due to the highly dispersed distribution of Ag on the flower-like CuO and higher vacancy O. Ag/3CuO exhibits higher FE H2 compared to other catalysts across a wide potential range, and its minimal impedance is attributed to its exceptional performance in the hydrogen evolution reaction . The proposed reaction pathway for the most effective catalysts 2Ag/2CuO, as determined by in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), involves the following steps: CO 2 →*CO 2 − → *COOH → *CO→ *CHO→ *OCHCHO→ *OCHCH 2 → C 2 H 4 . These findings demonstrate that controlling the surface structure can influence the local environment to enhance the efficiency of CO 2 electroreduction.
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Journal of Materials Research and Technology-JMR&T
·
2025
·
IF 6.6
Yuanming Zhou,Mingyang Li,Shuxin Li,Shuangxing Zhu,Ruizhi Liu,Maozhong Yi,Ke Peng
The oxide layer that forms on the surface of C/C composites matrix-modified with multiphase ultra-high temperature ceramics is generally loose and poorly bonded, limiting its effectiveness in enhancing the ablation resistance of C/C composites. In this study, C/C composites were matrix-modified using solid solution ceramic TaZr 2 C 3 -SiC and multiphase ceramic TaC-2ZrC-SiC, both with the same Zr/Ta ratio. The C/C-TaZr 2 C 3 -SiC and comparative sample C/C-TaC-2ZrC-SiC composites were prepared through a high-solid-loading slurry impregnation method combined with a precursor infiltration and pyrolysis process. The flexural properties were evaluated, and ablation tests were conducted under an oxyacetylene flame. Compared to C/C-TaC-2ZrC-SiC, the C/C-TaZr 2 C 3 -SiC sample exhibited superior flexural properties and ablation resistance. The flexural strength, elastic modulus, and fracture toughness improved by 10.80%, 29.75%, and 37.67%, respectively. The mass and linear ablation rates were reduced by up to 85.49% and 77.26%, respectively. The superior ablation resistance of C/C-TaZr 2 C 3 -SiC was attributed to the formation of the anti-ablation microstructure composed of the Ta-rich oxide binder phase and Zr-rich oxide skeleton phase in the Ta-Zr-O oxide layer. The microstructure enhanced the viscosity of the oxides and strengthened their interfacial bonding, effectively suppressing the splashing and consumption of surface oxides under high heat flux while preventing their accumulation in the brim ablation region. The oxide layer was more compact and tightly bonded to the composite surface, providing the composites with significantly improved ablation protection. These findings provide a novel and effective approach for further improving the ablation resistance of C/C composites.
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2025
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IF 6.2
Pengfei Lian,Zengji Yao,Guangwei Sun,Yao Li,Zihao Ma,Xing Wang,Ying Han
The abundant aromatic structures present in lignin render it a potential raw material for quinoline compounds. Consequently, the utilization of the vast reserves of lignin and the exploration of efficient, practical, and sustainable synthetic routes for quinoline compounds will be a significant development direction in the utilization of biomass resources. In this work, with the monomer model compounds of lignin and 2-aminobenzyl alcohol as raw materials, the feasibility of continuous-flow synthesis of quinoline derivatives was explored using a microchannel reactor. The study investigated the influence of various factors on the synthesis process of quinoline derivatives and characterized the product structures, including analyses such as HPLC, TOF-MS, 1 H-NMR, 13 C-NMR, and 2D-HSQC. The research results indicated that under the optimal conditions, the yields of 2-phenylquinoline, 4-(quinolin-2-yl)phenol, 4-(quinolin-2-yl)guaiacol, and 4-(quinolin-2-yl)syringol were 93.89%, 64.26%, 33.98%, and 41.30%, respectively. The research results demonstrated that it is feasible to construct the quinoline ring through reactions such as C-N bond condensation and C-C cyclization.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2018
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IF 11.698
Yi Liu,Yuliu Liu,Yi Zhang
Aqueous-phase hydrogenation of glucose to lower diols (ethylene glycol (EG), 1, 2-propylene glycol (PG), and butanediol (BDO)) over bi-functional Ru-W supported catalysts was investigated in a continuous-flow fixed-bed reactor. A variety of catalysts based on different supports including mesoporous SiO 2 , activated carbon (AC), carbon nanofibers (CNFs), and bulk WO 3 were compared and examined by N 2 physisorption, H 2 chemisorption, XRD, TEM, ICP, H 2 -TPR, in-situ / ex-situ XPS, NH 3 -TPD, and Raman spectra. The results indicate that the lower diols yield is highly dependent on the synergistic effect of Ru metal sites and WO x acid sites, in other words, strongly depending on the competitive reactions of the glucose. Abundant W 4+ and Ru° sites on Ru-W/SiO 2 catalysts with large specific surface area effectively catalyze the selective cleavage of the C C bonds in glucose and subsequent hydrogenation to lower diols, resulting in 100% glucose conversion as well as highest diols selectivity (87.3%) over 50 h reaction at 478 K and 4 MPa H 2 . Meanwhile, the Ru/WO 3 with much lower surface area forms more W 5+ species, which is advantageous to producing more EG products (55.9%) at the same reaction conditions.
研究领域:
催化化学
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生物质转化
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绿色化学
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多相催化
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能源化工
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ACS Sustainable Chemistry & Engineering
·
2026
·Vol. 14
·期 29
·13042-13055
·
IF 7.6
Lau Chun-Yin,Li Xinwei,Zhang Yanlin,Rangarajan Goutham,Tse Ho-Yin,Zhuang Huichuan,Leu Shao-Yuan,Farnood Ramin R.
In this study, an amorphous carbon-rich carbon nitride photocatalyst was prepared by nitric acid treatment of pyrolyzed melamine followed by nitrogen annealing. The resulting semiconductor material exhibited an up-shifted valence band that enhances the oxidizing power of photogenerated holes, enabling selective C α −C β bond cleavage of 2-phenoxy-1-phenylethanol (2-POE). Using 1.5 g L −1 of the optimized photocatalyst in acetonitrile, 2-POE underwent first-order conversion with a reaction rate of 2.55 h −1 under a 9 W blue LED light source. Product analysis showed the formation of benzaldehyde as the major product, confirming C−C bond scission with 93.1% selectivity. In addition, ring-opening reactions were observed, producing fumaric and maleic acids as the by-products. Photocatalytic depolymerization of organosolv lignin further demonstrated ring opening of the β-O-4 linking motifs, forming dicarboxylic acids analogous to those generated from 2-POE. These demonstrate a metal-free photocatalytic platform capable of promoting β-O-4 bond cleavage in lignin model compounds and inducing photocatalytic structural modification of organosolv lignin, accompanied by the formation of low-molecular-weight aliphatic dicarboxylic acids.
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CHINESE JOURNAL OF CATALYSIS
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2026
·
IF 17.2
Wenhui Li,Yangbo Liu,Yilin Zhang,Qingwen Yang,Hong Yang,Xiaowa Nie,Xinwen Guo
The hydrogenation of CO 2 into high-value-added chemicals represents one of the most effective strategies for mitigating the greenhouse effect and addressing the energy crisis. In this study, the incorporation of Pt into Co-based catalysts is utilized to modulate the CO competitive adsorption capacity and reaction pathways, thereby significantly enhances the C–C coupling and the selectivity of C 2+ hydrocarbons during CO 2 hydrogenation. The formation of PtCo alloy in the catalysts is confirmed by X-ray absorption spectroscopy, in-situ X-ray diffraction, X-ray photoelectron spectroscopy and scanning transmission electron microscopy analyses. The study reveals that the presence of PtCo alloy alters the competitive adsorption behavior of CO and CO 2 on the catalyst, and enables CO to replace CO 2 as the strongly adsorbed species on the catalyst. Density functional theory calculations demonstrate that the PtCo alloy exhibits enhanced CO adsorption energy and reduced formation energy barrier for formate compared with pure Co. This is responsible for the emergence of an additional formate pathway on the PtCo catalyst. Consequently, the 2%PtCo catalyst achieves a C 2+ selectivity of 18.5% under conditions of 350 °C and 3 MPa, markedly higher than the 1.9% over the pure Co catalyst. PtCo catalysts possesses 83.6 mmol·g –1 ·h –1 C 2+ yield, outperforming the Fe-based reference catalyst by a factor of 4. The study presents a novel catalyst design concept for increasing C 2+ selectivity through regulating the competitive adsorption between intermediate and reactant.
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CERAMICS INTERNATIONAL
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2025
·
IF 5.6
Yixin Zhao,Chenxi Guo,Lei Chen,Xin Yang,Qizhong Huang
CeB 6 modified C/C-SiC-ZrC composites were designed by using slurry infiltration and precursor infiltration and pyrolysis method combined with high temperature treatment. Experimental results show that both adding CeB 6 and heat treatment could improve the ablative performance of C/C-SiC-ZrC composites significantly. Thermal conductivity of the composites can be optimized by high temperature treatment, accelerating the heat transfer of the composites in the ablation process. The heat treated C/C-SiC-ZrC-CeB 6 composites with high content of CeB 6 exhibit enhanced ablation performance at about 2600 °C, and the mass and linear ablation rates of the composites are 0.37 mg/s and 3.33 μm/s, respectively. The phase transition of ZrO 2 phases was suppressed by (Zr 1-x Ce x )O 2 solid solution phases which were uniformly distributed at the grain boundaries of ZrO 2 grains, resulting in the superior stability of the ZrO 2 scales under the scouring of the oxyacetylene flame.
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ANALYTICAL CHEMISTRY
·
2017
·
IF 6.32
Yaoyao Zhao,Hansen Zhao,Xu Zhao,Jia Jia,Qiang Ma,Sichun Zhang,Xinrong Zhang,Hitoshi Chiba,Shu-Ping Hui,Xiaoxiao Ma
Unsaturated fatty acids (FAs) serve as nutrients, energy sources, and signaling molecules for organisms, which are the major components for a large variety of lipids. However, structural characterization and quantitation of unsaturated FAs by mass spectrometry remain an analytical challenge. Here, we report the coupling of epoxidation reaction of the C═C in unsaturated FAs and tandem mass spectrometry (MS) for rapid and accurate identification and quantitation of C═C isomers of FAs in a shotgun lipidomics approach. Epoxidation of the C═C leads to the production of an epoxide which, upon collision induced dissociation (CID), produces abundant diagnostic ions indicative of the C═C location. The total intensity of the same set of diagnostic ions for one specific FA C═C isomer was also used for its relative and absolute quantitation. The simple experimental setup, rapid reaction kinetics (<2 min), high reaction yield (>90% for monounsaturated FAs), and easy-to-interpret tandem MS spectra enable a promising methodology particularly for the analysis of unsaturated FAs in complex biological samples such as human plasma and animal tissues.
研究领域:
生物化学
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分析化学
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代谢组学
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TRANSPLANT IMMUNOLOGY
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2026
·
IF 1.6
Shaohua Wu,Xiao-ling Liang,Xunfeng Zou
Background Prolonged cold ischemia (pCI) is a well-established risk factor for both acute kidney injury and chronic allograft nephropathy (CAN). The chemokine C-C motif ligand 2 (CCL2) plays a pivotal role in sustaining chronic inflammation. This study aimed to elucidate the effect of pCI on functional role of CCL2 in the pathogenesis CAN in a rat model of renal transplantation. Method Isogenic (Lewis to Lewis) and allogenic (Fisher 344 to Lewis) kidney transplants (KTx) were performed, with donor kidneys subjected to cold storage for either 2 h or 12 h. Animals were thus divided into four groups: iso-2 h, iso-12 h, allo-2 h, and allo-12 h. In the allo-12 h group, a subset of recipients received the CCL2 inhibitor cenicriviroc (CVC) as the allo12h + CVC group. Recipients were monitored for up to 90 days post-transplantation. Results At day 90 post-implantation, allografts exhibited significant fibrosis and markedly impaired renal function in the animaols with pCI, as indicated by higher total Banff scores and lower creatinine clearance rates ( P < 0.05). In contrast, these changes were not evident in isografts with pCI. The levels of of macrophages and M1 activation in the Allo-12 h group were increased, as demonstrated by elevated expression levels of CD68 and inducible nitric oxide synthase (iNOS); which were significantly mitigated by CVC treatment. Furthermore, during the acute phase (day 7 post-surgery), pCI caused severe acute kidney injury and induced a higher infiltration of CD3 + lymphocytes in the allografts compared to the isografts ( P < 0.05). Additionally, the CCL2 receptor CCR2 positive cells showed a substantial increase in the Allo-12 h group, concomitant with upregulation of CCL2 expression in allografts compared to isografts. Conclusion Our study demonstrates that chemokine CCL2 involves in the development of CAN, through recruitment of inflammatory cells during the acute phase following surgery.
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PubMed
高影响因子
MACROMOLECULAR RESEARCH
·
2026
·
IF 3.7
Jia Yuan,Yang Ziyi,Yang Juxiang,Li Beibei,Liu Zhen
Hyperbranched polysiloxanes (HBPSi) are novel non-conjugated polymers with aggregation-induced emission (AIE) and modifiable terminals, and have attracted attention due to their unique topology and functional potential. In this study, two AIE-active HBPSi derivatives (OA-HBPSi and IBO-HBPSi, where OA stands for oleic acid and IBO stands for isobutyric acid) containing C=C and acyloxy groups were successfully synthesized via transesterification. Gel Permeation Chromatography (GPC) was used to characterize their molecular weight distributions; Fourier Transform Infrared Spectroscopy (FTIR) and solid-state Photoluminescence (PL) were employed to elucidate their structure-property relationships. Ultraviolet-Visible (UV-Vis) spectroscopy and fluorescence spectrophotometry were applied to investigate their AIE behavior under solvent concentration gradients, with a focus on luminescence mechanisms. The results showed a non-monotonic relationship between fluorescence intensity and the molecular weight (M w ) of HBPSi derivatives: fluorescence intensity is enhanced with moderate M w elevation but reduced at excessively high M w due to molecular packing effects and acyloxy group rotation. Notably, as the volume fraction of CCl 4 reached the range that induces significant polymer aggregation, the intensities of both excitation peaks (266–294 nm, UV region) and emission peaks (440–460 nm, blue visible region) increased exponentially—this trend reflects the dependence of blue luminescence on polymer aggregation degree, supporting the proposed cluster-induced emission hypothesis. Consistent with FTIR spectral shifts and solvent-dependent PL behavior, we propose a mechanism hypothesis: the AIE of these derivatives originates from the synergy of “non-conjugated functional group clusters” in the polymers. Cluster-induced electronic delocalization and intramolecular charge transfer (ICT) between C=C and acyloxy groups may facilitate exciton radiative transitions, while the 3D hyperbranched spatial hindrance restricts excessive intermolecular aggregation—collectively suppressing non-radiative transition pathways. Graphical abstract
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